Resin composition, method for producing heat-resistant resin film, and display device

ABSTRACT

A resin composition which is configured such that if the resin composition is formed into a resin composition film that has a thickness of 3.0 μm after a heat treatment at a temperature within the range of 200-350° C., the resin composition film forms a heat-resistant resin film that has a light transmittance of 50% or more at a wavelength of 365-436 nm before the heat treatment, while having a light transmittance of 10% or less at a wavelength of 365-436 nm after the heat treatment. Provided is a resin composition having a function of absorbing ultraviolet light and visible light in a short wavelength range, which is suitable for the formation of a planarization film, an insulating layer and a partition wall that are used for organic light emitting devices or display devices.

TECHNICAL FIELD

The present invention relates to a resin composition produced using acompound capable of developing a color by a heat treatment and a methodfor producing a heat-resistant resin film. The present invention alsorelates to a resin composition from which a heat-resistant resin filmthat can absorb ultraviolet light and visible light in a shortwavelength range can be formed. More specifically, the present inventionrelates to: a photosensitive resin composition which is suitable forapplications including a surface-protecting film or an interlayerinsulating film for semiconductor elements, an insulating layer fororganic electroluminescence (wherein an electroluminescence is referredto as an “EL”, hereinafter) elements, a planarization film for thin filmtransistor (wherein a thin film transistor is referred to as a “TFT”,hereinafter) substrates for driving display devices equipped withorganic EL elements, a protective/insulating film for wiring lines oncircuit boards, a planarization film for on-chip microlenses forsolid-state imaging elements, various displays/solid-state imagingelements, and a solder resist for circuit boards; and a method forproducing a heat-resistant resin film.

BACKGROUND ART

A cured film produced by curing a composition containing a polyimide ora polybenzoxazole has been widely used as an insulating film, aprotective film or a planarization film for semiconductor elements anddisplay devices, or the like. Particularly when used in a displaydevice, for example when used as an insulating layer for organic ELdisplays or a black matrix for liquid crystal displays, it is requiredto reduce the light transmittance of the cured film for the purpose ofimproving the contrast in the displays. Furthermore, for the purpose ofpreventing the deterioration or malfunctions of a display device or thedevelopment of a leakage current in the display device which can becaused by the penetration of light into TFTs for driving the displaydevice, an insulating layer in an organic EL display or a planarizationfilm to be provided on a TFT substrate in an organic EL display is alsorequired to have a reduced transmittance.

As an example of the technique for reducing the light transmittance tolight having a wavelength within a visible light wavelength range, whichis longer than 400 nm, in a cured film, a method can be mentioned inwhich a coloring agent such as carbon black, an organic or inorganicpigment or a dye is added to a resin composition, as employed in a blackmatrix material for liquid crystal displays and an RGB paste material. Aresin composition containing the coloring agent can absorb light havinga wavelength of 350 to 460 nm, and therefore is hardly used as apositive-working photosensitive resin composition which can bephotosensitized by exposing the composition to light in theabove-mentioned wavelength range so as to penetrate the light to thebottom of a resin film produced from the composition. For this reason,the resin composition is generally used as a negative-workingphotosensitive resin composition from which a film is produced byphotocuring from the surface thereof.

As examples of the technique for reducing the light transmittance of acured film produced from a positive-working photosensitive resincomposition, the following resin compositions can be mentioned: apositive-working radioactive resin composition which comprises analkali-soluble resin, a quinone diazide compound and a color-developingcomposition comprising, for example, a leuco dye and a color developer(see, e.g., Patent Document 1); a photosensitive resin to which aheat-sensitive material that can turn black upon the application of heatis added in advance (see, e.g., Patent Document 2); a positive-workingphotosensitive resin composition which comprises an alkali-solubleresin, a quinone diazide compound, a thermally color-developing compoundcapable of developing a color upon heating and having an absorptionmaximum at a wavelength of 350 to 700 nm inclusive, and a compoundhaving no absorption at a wavelength of 350 nm or more and less than 500nm and having an absorption maximum at a wavelength of 500 to 750 nminclusive (see, e.g., Patent Document 3); and a resin composition whichcomprises a polyimide, a polybenzoxazole, a polyimide precursor or apolybenzoxazole precursor, dihydroxynaphthalene and a thermalcrosslinking agent having a specific structure, and which ischaracterized in that the light transmittance of a cured film producedfrom the resin composition to light having a wavelength within a visiblelight wavelength range can be reduced while maintaining the lighttransmittance of an uncured resin film produced from the resincomposition (see, e.g., Patent Document 4). These are techniques inwhich a color-developing compound that can produce a color upon theapplication of an energy such as heat is used to reduce thetransmittance of a cured film while keeping the transmittance of anuncured resin film to light having a wavelength within an exposing-lightwavelength range at a high level.

When a color-developing compound that can produce a color upon theapplication of an energy such as heat is used, it becomes possible toreduce the (light) transmittance of a heat-resistant resin film, whichis a cured product of a resin film produced using the color-developingcompound, while keeping the (light) transmittance of the resin film thatis not cured yet to light having a wavelength within an exposing-lightwavelength range at a high level. Therefore, the color-developingcompound can impart both positive-working photosensitive properties andnegative-working photosensitive properties. In these techniques,however, it cannot be considered that the degree of the reduction in(light) transmittance of a cured heat-resistant resin film is asufficiently low value.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: Japanese Patent Laid-open Publication No. 2008-122501

Patent Document 2: Japanese Patent Laid-open Publication No. 10-170715

Patent Document 3: Japanese Patent Laid-open Publication No. 2004-326094

Patent Document 4: International Publication No. 2010/87238

SUMMARY OF THE INVENTION Problems to be Solved by the Invention

The present invention addresses the problem of providing a resincomposition which enables the formation of a heat-resistant resin filmthat has high sensitivity to ultraviolet light and visible light in ashort wavelength range and can be greatly reduced in transmittanceparticularly to light having a wavelength of 350 to 460 nm. The presentinvention also addresses the problem of providing a highly reliableorganic EL display which does not undergo malfunctions associated withthe penetration of light into the device, by using the resincomposition.

The present invention also addresses the problem of providing aphotosensitive resin composition which enables the formation of aheat-resistant resin film that is highly sensitive to ultraviolet lightand visible light in a short wavelength range and can be reduced intransmittance particularly to light having a wavelength of 365 to 436 nmby a heat treatment. The present invention also addresses the problem ofproviding a highly reliable organic EL display which does not undergomalfunctions associated with the penetration of light into the device,by using the photosensitive resin composition.

Solutions to the Problems

That is, a first aspect of the present invention is a resin compositionwhich is configured such that, when the resin composition is formed intoa resin composition film having a thickness of 2.0 μm after a heattreatment at a temperature within the range from 200 to 350° C., theresin composition film forms a heat-resistant resin film having a lighttransmittance of 50% or more at a wavelength of 365 to 436 nm before theheat treatment and having a light transmittance of 5% or less at awavelength of 350 to 460 nm after the heat treatment. The resincomposition is a resin composition having positive-workingphotosensitivity which contains a photo-acid generator. The presentinvention also provides a resin composition having positive-workingphotosensitivity and comprising (A1) a polyimide, a polybenzoxazole, apolyimide precursor or a polybenzoxazole precursor, (A3) a phenolicresin and/or a polyhydroxystyrene resin, (B) a thermallycolor-developing compound, (C) aphoto-acidgenerator, and (D) a solvent,wherein the component (A3) is contained in an amount of 5 to 50 parts byweight inclusive relative to 100 parts by weight of the component (A1).

The present invention also provides a resin composition havingpositive-working photosensitivity and comprising (A2) a resin havingsuch a backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, (A3) a phenolicresin and/or a polyhydroxystyrene resin, (B) a thermallycolor-developing compound, (C) aphoto-acidgenerator, and (D) a solvent,wherein the component (A3) is contained in an amount of 5 to 50 parts byweight inclusive relative to 100 parts by weight of the component (A2).

The present invention also provides a method for producing aheat-resistant resin film, comprising the steps of: applying the resincomposition onto a substrate to form a coating film; drying the coatingfilm; exposing the dried photosensitive resin film to light; developingthe light-exposed photosensitive resin film; and subjecting thedeveloped photosensitive resin film to a heat treatment.

The present invention also provides a display device comprising asubstrate, a first electrode which is formed on the substrate, aninsulating layer which is formed on the first electrode in such a manneras to allow the first electrode to be partially exposed to light, and asecond electrode which is provided opposed to the first electrode,wherein the insulating layer is a heat-resistant resin film produced bythe production method according to the present invention.

The present invention also provides a display device comprising asubstrate on which thin film transistors (TFTs) are formed, aplanarization film which is provided in such a manner as to coverprojections and depressions on the substrate, and display elements whichare provided on the planarization film, wherein the planarization filmis a heat-resistant resin film produced by the production methodaccording to the present invention.

A second aspect of the present invention is a resin composition which isconfigured such that, when the resin composition is formed into a resincomposition film that has a thickness of 3.0 μm after a heat treatmentat a temperature within the range from 200 to 350° C., the resincomposition film forms a heat-resistant resin film having a lighttransmittance of 50% or more at a wavelength of 365 to 436 nm before theheat treatment and having a light transmittance of 10% or less to lighthaving a wavelength of 365 to 436 nm after the heat treatment.

The present invention is a resin composition having positive-workingphotosensitivity which contains a photo-acid generator.

The present invention also provides a resin composition havingpositive-working photosensitivity and comprising (A) an alkali-solubleresin, (I) a compound whose maximum absorption wavelength shifts by aheat treatment, (C) a photo-acid generator, and (D) a solvent.

The present invention also provides a method for producing aheat-resistant resin film, comprising the steps of: applying the resincomposition onto a substrate to form a coating film; drying the coatingfilm; exposing the dried photosensitive resin film to light; developingthe light-exposed photosensitive resin film; and subjecting thedeveloped photosensitive resin film to a heat treatment.

The present invention also provides a display device comprising asubstrate, a first electrode which is formed on the substrate, aninsulating layer which is formed on the first electrode in such a manneras to allow the first electrode to be partially exposed to light, and asecond electrode which is provided opposed to the first electrode,wherein the insulating layer is a heat-resistant resin film produced bythe production method according to the present invention.

The present invention also provides a display device comprising asubstrate on which thin film transistors (TFTs) are formed, aplanarization film which is provided in such a manner as to coverprojections and depressions on the substrate, and display elements whichare provided on the planarization film, wherein the planarization filmis a heat-resistant resin film produced by the production methodaccording to the present invention.

Effects of the Invention

According to the first aspect of the present invention, it is possibleto provide a resin composition which enables the formation of aheat-resistant resin film that has high sensitivity to ultraviolet lightand visible light in a short wavelength range and can be greatly reducedin transmittance particularly to light having a wavelength of 350 to 460nm by a heat treatment. An organic EL display equipped with aheat-resistant resin film produced using the resin composition of thepresent invention does not undergo deterioration or malfunctions, thedevelopment of a leakage current therein or the like which can be causedby the penetration of light into TFTs for driving the device. Therefore,the resin composition is suitable for the improvement in reliability ofan organic EL display.

According to the second aspect of the present invention, it is possibleto provide a resin composition which enables the formation of aheat-resistant resin film that is highly sensitive to ultraviolet lightand visible light in a short wavelength range, allows the penetration ofultraviolet light and visible light in a short wavelength rangetherethrough before a heat treatment, and is reduced in transmittanceparticularly to light having a wavelength of 365 to 436 nm by a heattreatment. An organic EL display equipped with a heat-resistant resinfilm produced using the resin composition of the present invention doesnot undergo deterioration or malfunctions, the development of a leakagecurrent therein or the like which can be caused by the penetration oflight into TFTs for driving the device. Therefore, the resin compositionis suitable for the improvement in reliability of an organic EL display.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a cross-sectional view of a TFT substrate.

EMBODIMENTS OF THE INVENTION

The present invention is categorized into the following two aspects.

A first aspect of invention is a resin composition which is configuredsuch that, when the resin composition is formed into a resin compositionfilm having a thickness of 2.0 μm after a heat treatment at atemperature within the range from 200 to 350° C., the resin compositionfilm forms a heat-resistant resin film having a light transmittance of50% or more at a wavelength of 365 to 436 nm before the heat treatmentand having a light transmittance of 5% or less at a wavelength of 350 to460 nm after the heat treatment.

It is preferred that the resin composition according to the presentinvention contains a photo-acid generator to impart positive-workingphotosensitivity to the resin composition. It is also preferred that theresin composition according to the present invention contains a dyeand/or a pigment, because the resin composition becomes able to absorbvisible light in the whole wavelength range and therefore acontrast-improving effect can also be imparted to the resin composition.

The present invention also provides a resin composition comprising (A1)a polyimide, a polybenzoxazole, a polyimide precursor or apolybenzoxazole precursor, (A3) a phenolic resin and/or apolyhydroxystyrene resin, (B) a thermally color-developing compound, (C)a photo-acid generator, and (D) a solvent, wherein the component (A3) iscontained in an amount of 5 to 50 parts by weight inclusive relative to100 parts by weight of the component (A1).

The present invention also provides a resin composition havingpositive-working photosensitivity and comprising (A2) a resin havingsuch a backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, (A3) a phenolicresin and/or a polyhydroxystyrene resin, (B) a thermallycolor-developing compound, (C) aphoto-acidgenerator, and (D) a solvent,wherein the component (A3) is contained in an amount of 5 to 50 parts byweight inclusive relative to 100 parts by weight of the component (A2).

A second aspect of invention is a resin composition which is configuredsuch that, when the resin composition is formed into a resin compositionfilm that has a thickness of 3.0 μm after a heat treatment at atemperature within the range from 200 to 350° C., the resin compositionfilm forms a heat-resistant resin film having a light transmittance of50% or more at a wavelength of 365 to 436 nm before the heat treatmentand having a light transmittance of 10% or less to light having awavelength of 365 to 436 nm after the heat treatment.

It is preferred that the resin composition according to the presentinvention contains a compound which does not have an absorption maximumat a wavelength of 340 nm or more and less than 436 nm and has anabsorption maximum at a wavelength of 436 to 750 nm inclusive, becausethe resin composition becomes able to absorb visible light in the wholewavelength range and therefore a contrast-improving effect can also beimparted to the resin composition. It is also preferred that the resincomposition according to the present invention contains a photo-acidgenerator and therefore has positive-working photosensitivity.

The present invention also provides a resin composition havingpositive-working photosensitivity and comprising (A) an alkali-solubleresin, (I) a compound whose maximum absorption wavelength shifts by aheat treatment, (C) a photo-acid generator, and (D) a solvent.

Hereinbelow, the present invention will be described in detail.

First, the first aspect of the invention will be described in detail.

The present invention relates to a resin composition which is configuredsuch that, when the resin composition is formed into a resin compositionfilm having a thickness of 2.0 μm after a heat treatment at atemperature within the range from 200 to 350° C., the resin compositionfilm forms a heat-resistant resin film having a light transmittance of50% or more at a wavelength of 365 to 436 nm before the heat treatmentand having a light transmittance of 5% or less at a wavelength of 350 to460 nm after the heat treatment. The term “heat-resistant resin” as usedherein refers to a resin which produces a reduced degassing amount undera high temperature of 200° C. or higher after being cured by a heattreatment and has excellent heat resistance. Examples of theheat-resistant resin include, but not limited to, a polyimide, apolybenzoxazole, a polyimide precursor, a polybenzoxazole precursor, aresin having such a backbone structure that two cyclic structures arebonded to a cyclic-structure-constituting quaternary carbon atom, acyclic olefin polymer, and a polysiloxane. Two or more of these resinsmay be contained. The term “resin composition from which aheat-resistant resin film can be formed which has a light transmittanceof 5% or less to light having a wavelength of 350 to 460 nm after theheat treatment” refers to a resin composition from which aheat-resistant resin film can be formed which has a transmittance of 5%or less to light having a wavelength of 350 to 460 nm after a heattreatment at a temperature of 200 to 350° C. An organic EL display orthe like equipped with the heat-resistant resin film does not undergodeterioration or malfunctions, the development of a leakage currenttherein or the like which can be caused by the penetration of light intoTFTs for driving the device. Therefore, the resin composition has aneffect of improving the reliability of an organic EL display or thelike. When the heat-resistant resin film does not have a thickness of2.0 μm after a heat treatment, the light transmittance of theheat-resistant resin film can be determined by converting the thicknessof the heat-resistant resin film to 2.0 μm in accordance with theLambert's law.

It is preferred that the resin composition according to the presentinvention contains a photo-acid generator to impart positive-workingphotosensitivity to the resin composition. It is also preferred that theresin composition according to the present invention contains a dyeand/or a pigment, because the resin composition becomes able to absorbvisible light in the whole wavelength range and therefore acontrast-improving effect can also be imparted to the resin composition.

The present invention also relates to a resin composition comprising(A1) a polyimide, a polybenzoxazole, a polyimide precursor or apolybenzoxazole precursor, (A3) a phenolic resin and/or apolyhydroxystyrene resin, (B) a thermally color-developing compound, (C)a photo-acid generator, and (D) a solvent, wherein the component (A3) iscontained in an amount of 5 to 50 parts by weight inclusive relative to100 parts by weight of the component (A1).

The present invention also relates to a resin composition havingpositive-working photosensitivity and comprising (A2) a resin havingsuch a backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, (A3) a phenolicresin and/or a polyhydroxystyrene resin, (B) a thermallycolor-developing compound, (C) a photo-acid generator, and (D) asolvent, wherein the component (A3) is contained in an amount of 5 to 50parts by weight inclusive relative to 100 parts by weight of thecomponent (A2).

The resin composition according to the present invention contains (A1) apolyimide, a polybenzoxazole, a polyimide precursor or a polybenzoxazoleprecursor.

These resins produce a small degassing amount under a high temperatureof 200° C. or higher after a heat treatment, have excellent heatresistance, and can exhibit excellent properties for use as aplanarization film or an insulating layer used in organic light emittingdevices and display elements or for the formation of a partition wall inthe devices.

With respect to the component (A1) to be used in the present invention,the polyimide is not particularly limited as long as it has an imidering, and the polybenzoxazole is not particularly limited as long as ithas a benzoxazole ring. The polyimide precursor is not particularlylimited as long as it has a structure that can be dehydrated andring-closed to produce a polyimide having an imide ring. Thepolybenzoxazole precursor is not particularly limited as long as it hasa structure that can be dehydrated and ring-closed to produce apolybenzoxazole having a benzoxazole ring. In the present invention, thecomponent (A1) is more preferably a polyimide precursor or apolybenzoxazole precursor, and more preferably contains a structuralunit represented by general formula (1) as the main component.

In general formula (1), R¹ and R² may be the same as or different fromeach other, and independently represent a bivalent to octavalent organicgroup having 2 or more carbon atoms. The bivalent to octavalent organicgroup having 2 or more carbon atoms may be a group in which —CH₂— issubstituted by —CO—, —COO—, —NH—, —NHCO—, —O—, —S—, —SO₂—, —Si— or—Si(CH₃)₂—, or may be a group in which a hydrogen atom contained thereinis substituted by a fluoroalkyl group, a hydroxyl group, an alkoxylgroup, a nitro group, a cyano group, a fluorine atom, a chlorine atom or—COOR¹′. R¹′ represents a hydrogen atom or an alkyl group having 1 to 20carbon atoms. R³ and R⁴ may be the same as or different from each other,and independently represent a hydrogen atom or an alkyl group having 1to 20 carbon atoms. a and b independently represent an integer of 0 to4, and c and d independently represent an integer of 0 to 2. Providedthat a+b>0.

The above-shown general formula (1) represents a polyimide precursor ora polybenzoxazole precursor each having a hydroxyl group, which hassuperior solubility in an aqueous alkaline solution due to the presenceof the hydroxyl group, compared with a polyimide precursor or apolybenzoxazole precursor each having no hydroxyl group.

Each of the polyimide precursor and the polybenzoxazole precursor is aresin having an amide bond in the main chain thereof, and is generallycomposed of an amine component and an acid component. Each of thepolyimide precursor and the polybenzoxazole precursor can be dehydratedand ring-closed by a heat treatment or a chemical treatment to producethe above-mentioned polyimide or polybenzoxazole. The number of repeatsof the structural unit in the present invention is preferably 10 to100000. Specific examples of the polyimide precursor include a polyamicacid ester and a polyisoimide, and a polyamic acid ester is preferred.Specific examples of the polybenzoxazole precursor include apolyhydroxyamide, a polyaminoamide, a polyamide and a polyamideimide,and a polyhydroxyamide is preferred. In each of the polyimide precursorand the polybenzoxazole precursor, it is preferred that an acid residueor an amine residue has an acidic group or an acidic group derivativesuch as OR⁵, SO₃R⁵, CONR⁵R⁶, COOR⁵ and SO₂NR⁵R⁶, more preferably ahydroxyl group, from the viewpoint of the solubility in an aqueousalkaline solution. R⁵ and R⁶ independently represent a hydrogen atom, ahydrocarbon group having 1 to 20 carbon atoms or a group having such astructure that a hydrogen atom in a hydrocarbon group having 1 to 20carbon atoms is substituted by another type of atom. The term “acidicgroup” refers to a case where all of R⁵'s or R⁶'s are hydrogen atoms,and the term “acidic group derivative” refers to a case where ahydrocarbon group having 1 to 20 carbon atoms or a group having such astructure that a hydrogen atom in a hydrocarbon group having 1 to 20carbon atoms is substituted by another type of atom is contained in R⁵or R⁶.

In the present invention, preferred examples of the structure of an acidcomponent to be used in the production of the polyimide precursor andthe polybenzoxazole precursor are shown below. Structures in each ofwhich 1 to 4 hydrogen atoms is substituted by an alkyl group having 1 to20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group,a nitro group, a cyano group, a fluorine atom or a chlorine atom canalso be included in the preferred examples.

In the formulae, J represents a direct bond, —COO—, —CONH—, —CH₂—,—C₂H₄—, —O—, —C₃H₆—, —SO₂—, —S—, —Si(CH₃)₂—, —O—Si(CH₃)₂—O—, —C₆H₄—,—C₆H₄—O—C₆H₄—, —C₆H₄—C₃H₆—C₆H₄— or —C₆H₄—C₃F₆—C₆H₄—.

Examples of the acid component to be used in the production of thepolyimide precursor and the polybenzoxazole precursor include adicarboxylic acid, a tricarboxylic acid and a tetracarboxylic acid.

Preferred examples of the dicarboxylic acid include terephthalic acid,isophthalic acid, diphenyl ether dicarboxylic acid,bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid,benzophenone dicarboxylic acid and triphenyldicarboxylic acid.

Examples of the tricarboxylic acid may include trimellitic acid,trimesic acid, diphenylethertricarboxylic acid, andbiphenyltricarboxylic acid.

Examples of the tetracarboxylic acid may include aromatictetracarboxylic acids such as pyromellitic acid,3,3′,4,4′-biphenyltetracarboxylic acid,2,3,3′,4′-biphenyltetracarboxylic acid,2,2′,3,3′-biphenyltetracarboxylic acid,3,3′,4,4′-benzophenonetetracarboxylic acid,2,2′,3,3′-benzophenonetetracarboxylic acid,2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane,2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane,1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane,bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane,bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether,1,2,5,6-naphthalenetetracarboxylic acid,2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylicacid, and 3,4,9,10-perylenetetracarboxylic acid, and aliphatictetracarboxylic acids such as butanetetracarboxylic acid and1,2,3,4-cyclopentanetetracarboxylic acid.

It is more preferred to use an acid produced by substituting each of theabove-exemplified dicarboxylic acids, tricarboxylic acids andtetracarboxylic acids by 1 to 4 acidic groups or acidic groupderivatives (e.g., OR⁵ groups, SO₃R⁵ groups, CONR⁵R⁶ groups, COOR⁵groups and SO₂NR⁵R⁶ groups), preferably 1 to 4 hydroxyl groups orsulfonic acid groups, sulfonic acid amide groups, sulfonic acid estergroups or the like. R⁵ and R⁶ independently represent a hydrogen atom ora monovalent hydrocarbon group having 1 to 20 carbon atoms.

Each of these acids may be used without any modification or withmodification into an acid anhydride or an active ester. These acids maybe used singly, or two or more of them may be used in combination.

A silicon-atom-containing tetracarboxylic acid, such asdimethylsilanediphthalic acid and 1,3-bis(phthalicacid)tetramethyldisiloxane, can also be used to improve the bonding to asubstrate and the resistance to oxygen plasma to be used in washing orthe like or a UV ozone treatment. It is preferred that thesilicon-atom-containing tetracarboxylic acid is used in an amount of0.0130 mol % relative to the total amount of the acid components.

In the present invention, examples of the preferred structure of theamine component to be used in the production of the polyimide precursoror the polybenzoxazole precursor are shown below. In addition, variantsof the structures, in each of which 1 to 4 hydrogen atoms areindependently substituted by an alkyl group having 1 to 20 carbon atoms,a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, acyano group, a fluorine atom or a chlorine atom are also preferred.

In the formulas, J represents a direct bond, —CO—, —COO—, —CONH—,—C₂H₄—, —O—, —C₃H₆—, —C₃F₆—, —SO₂—, —Si(CH₃)₂—, —O—Si(CH₃)₂—O—, —C₆H₄—,—C₆H₄—O—C₆H₄—, —C₆H₄—C₃H₆—C₆H₄— or —C₆H₄—C₃F₆—C₆H₄—. R⁷ to R⁹independently represent a hydrogen atom or a monovalent hydrocarbongroup having 1 to 20 carbon atoms, and are preferably monovalent alkylgroups each having 1 to 20 carbon atoms.

As the amine component to be used in the production of the polyimideprecursor and the polybenzoxazole precursor, a diamine can be used.

Preferred examples of the diamine may include hydroxyl group-containingdiamines such as bis(3-amino-4-hydroxyphenyl)hexafluoropropane,bis(3-amino-4-hydroxyphenyl)sulfone,bis(3-amino-4-hydroxyphenyl)propane,bis(3-amino-4-hydroxyphenyl)methylene,bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl,bis(3-amino-4-hydroxyphenyl)fluorene, carboxyl group-containing diaminessuch as 3,5-diaminobenzoic acid and 3-carboxy-4,4′-diaminodiphenylether, sulfonic acid-containing diamines such as 3-sulfonicacid-4,4-diaminodiphenyl ether, dithiohydroxyphenylenediamine,3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether,3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone,3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide,1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine,p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine,bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone,bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)ether,1,4-bis(4-aminophenoxy)benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl,2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl,3,3′-diethyl-4,4′-diaminobiphenyl,2,2′,3,3′-tetramethyl-4,4′-diaminobiphenyl,3,3′,4,4′-tetramethyl-4,4′-diaminobiphenyl,2,2′-di(trifluoromethyl)-4,4′-diaminobiphenyl, or compounds eachresulting from replacing some hydrogen atoms of the aromatic ring ofeach of the foregoing by an alkyl group or a halogen atom, and aliphaticdiamines such as cyclohexyldiamine and methylenebiscyclohexylamine. Eachof these diamines may be substituted by an alkyl group having 1 to 10carbon atoms (e.g., a methyl group, an ethyl group), a fluoroalkyl grouphaving 1 to 10 carbon atoms (e.g., a trifluoromethyl group), or a groupsuch as F, Cl, Br and I. Each of the above-exemplified diaminespreferably has an acidic group or an acidic group derivative (e.g., OR⁵,SO₃R⁵, CONR⁵R⁶, COOR⁵, SO₂NR⁵R⁶), and more preferably has a hydroxylgroup. R⁵ and R⁶ independently represent a hydrogen atom or a monovalenthydrocarbon group having 1 to 20 carbon atoms.

These diamines may be used without any modification, or diisocyanatecompounds and trimethylsilylated diamines corresponding to the diaminesmay be used, and two or more of them may be used in combination. Inapplications in which heat resistance is required, it is preferred touse an aromatic diamine in an amount of 50 mol % or more relative to thetotal amount of the diamine components.

As the diamine component, a silicon-atom-containing diamine, such as1,3-bis(3-aminopropyl)tetramethyldisiloxane and1,3-bis(4-anilino)tetramethyldisiloxane, can also be used to improve thebonding to a substrate and the resistance to oxygen plasma to be used inwashing or the like or a UV ozone treatment. It is preferred that thesilicon-atom-containing diamine is used in an amount of 1 to 30 mol %relative to the total amount of the diamine components.

In the present invention, it is preferred to cap a terminal of thepolyimide precursor or the polybenzoxazole precursor by a monoamine, anacid anhydride, an acid chloride or a monocarboxylic acid each having ahydroxyl group, a carboxyl group, a sulfonic acid group or a thiolgroup. Two or more of these capping substances may be used incombination. When the resin has the above-mentioned group at a terminalthereof, it becomes possible to easily adjust the dissolution rate ofthe resin in an aqueous alkaline solution to a value within a desirablerange.

Examples of the monoamine include aniline, naphthylamine, andaminopyridine, compounds having a phenolic hydroxyl group, such as3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol,4-aminophenol, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline,1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene,1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene,1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene,1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene,2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene,2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene,2-hydroxy-3-aminonaphthalene, and 1-amino-2-hydroxynaphthalene,compounds having a carboxyl group, such as 1-carboxy-8-aminonaphthalene,1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene,1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene,1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene,1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene,2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene,2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene,1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinicacid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylicacid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-O-toluicacid, ammelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoicacid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, and4-aminobenzenesulfonic acid, and compounds having a thiol group, such as5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline,1-mercapto-8-aminonaphthalene, 1-mercapto-7-amino-naphthalene,1-mercapto-6-amino-naphthalene, 1-mercapto-5-aminonaphthalene,1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene,1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene,2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene,2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene,2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene,3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol,and 4-aminothiophenol.

Among them, preferred examples of the monoamine may include5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene,1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene,1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene,2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene,1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene,1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene,2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene,2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid,4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid,2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid,4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine,2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol,3-aminothiophenol, and 4-aminothiophenol. These monoamines may be usedsingly, or two or more of them may be used in combination.

Examples of the acid anhydride, the acid chloride, and themonocarboxylic acid include acid anhydrides such as phthalic anhydride,maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride,and 3-hydroxyphthalic anhydride, monocarboxylic acids such as2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol,3-carboxythiophenol, 4-carboxythiophenol,1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene,1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene,1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene,1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene,1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene,1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene,1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene,2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, and4-carboxybenzenesulfonic acid, and monoacid chloride compounds with thecarboxyl group of the monocarboxylic acid formed into an acid chloride,monoacid chloride compounds with only one carboxy group of dicarboxylicacids such as terephthalic acid, phthalic acid, maleic acid,cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid,5-norbornene-2,3-dicarboxylic acid, 1, 2-dicarboxynaphthalene,1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene,1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene,1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene,2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and2,7-dicarboxynaphthalene formed into an acid chloride, and active estercompounds obtained by reaction of a monoacid chloride compound withN-hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3-dicarboxyimide.

Among them, preferred examples of the acid anhydride, the acid chloride,and the monocarboxylic acid may include acid anhydrides such as phthalicanhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylicanhydride, and 3-hydroxyphthalic anhydride, monocarboxylic acids such as3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol,4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene,1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene,1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene,1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, and4-carboxybenzenesulfonic acid, monoacid chloride compounds with thecarboxyl group of the monocarboxylic acid formed into an acid chloride,monoacid chloride compounds with only one carboxy group of dicarboxylicacids such as terephthalic acid, phthalic acid, maleic acid,cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene,1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and2,6-dicarboxynaphthalene formed into an acid chloride, and active estercompounds obtained by reaction of a monoacid chloride compound withN-hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3-dicarboxyimide.These monoamines may be used singly, or two or more of them may be usedin combination.

The content of the terminal-capping agent (e.g., a monoamine, an acidanhydride, an acid chloride, a monocarboxylic acid) is preferably 0.1 to70 mol %, more preferably 5 to 50 mol %, relative to the number of molesof the acid component monomer or the diamine component monomer to becharged. When the content is adjusted to the above-mentioned value, itbecomes possible to produce a resin composition which has a propersolution viscosity during the application of the resin composition andcan exert excellent film properties.

The resin may also have a polymerizable functional group at a terminalthereof. Examples of the polymerizable functional group include anethylenically unsaturated bond group, an acethylene group, a methylolgroup and an alkoxymethyl group.

The terminal-capping agent introduced into the resin can be detectedeasily by the following methods. For example, the resin having theterminal-capping agent introduced thereinto is dissolved in an acidicsolution to decompose the resin into an amine component and an acidcomponent which are constituent units of the resin, and these componentsare subjected to a measurement by gas chromatography (GC) or NMR todetect the terminal-capping agent easily. Alternatively, the resinhaving the terminal-capping agent introduced thereinto may be directlysubjected to a measurement by thermal decomposition gas chromatography(PGC) or infrared or ¹³C-NMR spectroscopy to detect the terminal-cappingagent.

The reaction solvent which can be used preferably in the synthesis ofthe polyimide, the polybenzoxazole, the polyimide precursor or thepolybenzoxazole precursor in the present invention is not particularlylimited, as long as the polymer can be synthesized. Specific examples ofthe reaction solvent include: a polar aprotic solvent, such asN-methyl-2-pyrrolidone, 7-butyrolactone, N,N-dimethylformamide,N,N-dimethylacetamide and dimethyl sulfoxide; a glycol ether, such astetrahydrofuran, dioxane, propylene glycol monomethyl ether, propyleneglycol monoethyl ether, diethylene glycol dimethyl ether, diethyleneglycol diethyl ether and diethylene glycol ethyl methyl ether; a ketone,such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetonealcohol; an ester, such as ethyl acetate, butyl acetate, isobutylacetate, propyl acetate, propylene glycol monomethyl ether acetate,glycol ether acetate and 3-methyl-3-methoxy butyl acetate; an alcohol,such as ethyl lactate, methyl lactate, diacetone alcohol and3-methyl-3-methoxybutanol; and an aromatic hydrocarbon, such as tolueneand xylene. Two or more of these solvents may be contained. The contentof the solvent is preferably 100 to 2000 parts by weight relative to thetotal amount, i.e., 100 parts by weight, of the compound having an aminogroup and the compound having an acid anhydride group.

The resin composition according to the present invention contains (A2) aresin having such a backbone structure that two cyclic structures arebonded to a cyclic-structure-constituting quaternary carbon atom. Theresin having such a backbone structure that two cyclic structures arebonded to a cyclic-structure-constituting quaternary carbon atom is aresin having such a backbone structure that two cyclic structures arebonded to a cyclic-structure-constituting quaternary carbon atom, i.e.,a cardo structure. A common cardo structure is a structure in which abenzene ring is bonded to a fluorene ring.

Specific examples of the backbone structure in which two cyclicstructures are bonded to a cyclic-structure-constituting quaternarycarbon atom include a fluorene backbone, a bisphenolfluorene backbone, abisaminophenylfluorene backbone, a fluorene backbone having an epoxygroup, and a fluorene backbone having an acryl group.

The resin having such a backbone structure that two cyclic structuresare bonded to a cyclic-structure-constituting quaternary carbon atom canbe produced by polymerizing a backbone having the cardo structurethrough a reaction between functional groups bonding to the backbones orthe like. The resin having such a backbone structure that two cyclicstructures are bonded to a cyclic-structure-constituting quaternarycarbon atom has a structure in which the main chain is linked to ahighly bulky side chain through one element (i.e., a cardo structure),and has a cyclic structure in the direction substantially perpendicularto the main chain.

Specific example of the monomer having a cardo structure include: acardo-structure-containing bisphenol, such as abis(glycidyloxyphenyl)fluorene-type epoxy resin,9,9-bis(4-hydroxyphenyl)fluorene and9,9-bis(4-hydroxy-3-methylphenyl)fluorene; a9,9-bis(cyanoalkyl)fluorene, such as 9,9-bis(cyanomethyl)fluorene; and a9,9-bis(aminoalkyl)fluorene, such as 9,9-bis(3-aminopropyl)fluorene.

The resin having such a backbone structure that two cyclic structuresare bonded to a cyclic-structure-constituting quaternary carbon atom isa polymer produced by polymerizing a monomer having a cardo structure,and may also be a copolymer of the monomer with another copolymerizablemonomer.

As the method for polymerizing the monomer, any conventional method canbe employed. Examples of the method include a ring openingpolymerization method and an addition polymerization method.

The resin composition according to the present invention mayadditionally contain a cyclic olefin polymer. Examples of the cyclicolefin polymer that can be used in the present invention include ahomopolymer and a copolymer of a cyclic olefin monomer having a cyclicstructure (an alicyclic or aromatic structure) and a carbon-carbondouble bond. The cyclic olefin polymer may also have a monomer otherthan the cyclic olefin monomer.

Examples of the monomer constituting the cyclic olefin polymer include acyclic olefin monomer having a protic polar group, a cyclic olefinmonomer having an aprotic polar group, a cyclic olefin monomer having nopolar group, and a monomer other than a cyclic olefin. The monomer otherthan a cyclic olefin may have a protic polar group or another polargroup, or may have no polar group.

Specific examples of the cyclic olefin monomer having a protonic polargroup include carboxyl group-containing cyclic olefins such as5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5-carboxymethyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5-exo-6-end-dihydroxycarbonylbicyclo[2.2.1]hept-2-ene,8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,and8-exo-9-end-dihydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,and hydroxyl group-containing cyclic olefins such as5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene,5-methyl-5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene,8-(4-hydroxyphenyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene, and8-methyl-8-(4-hydroxyphenyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene.These monomers may be used singly, or two or more of them may be used incombination.

Specific examples of the cyclic olefin monomer having a polar groupother than a protonic polar group include cyclic olefins having an estergroup such as 5-acetoxybicyclo[2.2.1]hept-2-ene,5-methoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene,8-acetoxytetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-ethoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-n-propoxycarbonyltetracyclo[4.4.0.11^(2,5).1^(7,10)]dodeca-3-ene,8-isopropoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-n-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-ethoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-n-propoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-isopropoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,and8-methyl-8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.1^(2,5),1^(7,10)]dodeca-3-ene,cyclic olefins having an N-substituted imide group such asN-phenyl-(5-norbornene-2,3-dicarboximide), cyclic olefins having a cyanogroup such as 8-cyanotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-cyanotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene, and5-cyanobicyclo[2.2.1]hept-2-ene, and cyclic olefins having a halogenatom such as 8-chlorotetracyclo[4.4.0.1^(2,5)1^(7,10)]dodeca-3-ene and8-methyl-8-chlorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene. Thesemonomers may be used singly, or two or more of them may be used incombination.

Specific examples of the cyclic olefin monomer having no polar groupinclude bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene,5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene,5-methylidene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-enetricyclo[4.3.0.1^(2,5)]deca-3,7-diene,tetracyclo[8.4.0.1^(11,14).0^(3,7)]pentadeca-3,5,7,12,11-pentaene,tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-ethyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methylidene-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-ethylidene-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-vinyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-propenyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,pentacyclo[6.5.1.1^(3,6).0^(2,7).0^(9,13)]pentadeca-3,10-diene,cyclopentene, cyclopentadiene,1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene,8-phenyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,tetracyclo[9.2.1.0^(2,10).0^(3,8)]tetradeca-3,5,7,12-tetraene,pentacyclo[7.4.0.1^(3,6).1^(10,13).0^(2,7)]pentadeca-4,11-diene, andpentacyclo[9.2.1.14,7.0^(2,10).0^(3,8)]pentadeca-5,12-diene. Thesemonomers may be used singly, or two or more of them may be used incombination.

Specific examples of the monomer other than the cyclic olefins includeα-olefins having 2 to 20 carbon atoms such as ethylene, propylene,1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene,3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene,4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene,3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, and 1-eicosene, and chain olefins such asnon-conjugated dienes including 1,4-hexadiene, 4-methyl-1,4-hexadiene,5-methyl-1,4-hexadiene, and 1,7-octadiene. These monomers may be usedsingly, or two or more of them may be used in combination.

As the method for polymerizing the cyclic olefin polymer using theabove-mentioned monomer, any conventional method can be employed.Examples of the method include a ring opening polymerization method andan addition polymerization method.

The polymerization catalyst to be used in the polymerization ispreferably a complex of a metal such as molybdenum, ruthenium or osmium.These polymerization catalysts may be used singly, or two or more ofthem may be used in combination.

The hydrogenation of the cyclic olefin polymer produced by thepolymerization of the monomer is generally carried out using ahydrogenation catalyst. As the hydrogenation catalyst, one which isconventionally used in the hydrogenation of an olefin compound can beused. Specific examples of the hydrogenation catalyst to be used includea Ziegler-type homogeneous catalyst, a noble metal complex catalyst anda supported noble metal-based catalyst.

Among these hydrogenation catalysts, noble metal complex catalysts ofrhodium, ruthenium and the like are preferred, and a ruthenium catalystwith which a nitrogenated heterocyclic carbene compound or phosphine,which is a compound having a high electron-donating property,coordinates is particularly preferred, from the viewpoint of avoidingthe occurrence of a side reaction causing the deformation of afunctional group or the like and enabling the selective hydrogenation ofa carbon-carbon unsaturated bond in the polymer.

The resin composition according to the present invention mayadditionally contain a polysiloxane. An example of the polysiloxane thatcan be used in the present invention is a polysiloxane produced by thehydrolytic condensation of at least one organosilane.

Specific examples of the organosilane include tetra-functional silanessuch as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, andtetraphenoxysilane, tri-functional silanes such asmethyltrimethoxysilane, methyltriethoxysilane,methyltriisopropoxysilane, methyltri-n-butoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane,ethyltri-n-butoxysilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, n-butyltrimethoxysilane,n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane,decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane,p-hydroxyphenyltrimethoxysilane,1-(p-hydroxyphenyl)ethyltrimethoxysilane,2-(p-hydroxyphenyl)ethyltrimethoxysilane,4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane,trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane,3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropyltriethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltriethoxysilane,[(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane,[(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane,3-mercaptopropyltrimethoxysilane, 3-(trimethoxysilyl)propyl succinate,1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane,1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane,1-anthracenyltrimethoxysilne, 9-anthracenyltrimethoxysilne,9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane,2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane,2-indenyltrimethoxysilane, and 5-acenaphthenyltrimethoxysilane,di-functional silanes such as dimethyldimethoxysilane,dimethyldiethoxysilane, dimethyldiacetoxysilane,di-n-butyldimethoxysilane, diphenyldimethoxysilane,(3-glycidoxypropyl)methyldimethoxysilane,(3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane,and di(1-naphthyl)diethoxysilane, and mono-functional silanes such astrimethylmethoxysilane, tri-n-butylethoxysilane,(3-glycidoxypropyl)dimethylmethoxysilane, and(3-glycidoxypropyl)dimethylethoxysilane. Two or more of theseorganosilanes may be used in combination.

Specific examples of the organosilane oligomer include: methyl silicate51 (n: 4 on average) manufactured by Fuso Chemical Co., Ltd., M silicate51 (n: 3 to 5 on average), silicate 40 (n: 4 to 6 on average) andsilicate 45 (n: 6 to 8 on average) manufactured by Tama Chemicals Co.,Ltd., and methyl silicate 51 (n: 4 on average), methyl silicate 53A (n:7 on average) and ethyl silicate 40 (n: 5 on average) manufactured byColcoat Co., Ltd. These products can be purchased from these companies.Two or more of them may be used in combination.

The content of an Si atom derived from the organosilane in thepolysiloxane can be determined by determining the structure of a rawmaterial organosilane by ¹H-NMR, ¹³C-NMR, ²⁹Si-NMR, IR, TOF-MS or thelike and then calculating an integration ratio of a peak coming from anSi—C bond to a peak coming from an Si—O bond in IR spectra of thestructure.

The weight average molecular weight (Mw) of the polysiloxane is notparticularly limited, and is preferably 1,000 or more as determined interms of polystyrene by GPC (gel permeation chromatography), from theviewpoint of improving the coating film formability. On the other hand,the weight average molecular weight (Mw) is preferably 100,000 or less,more preferably 50,000 or less, from the viewpoint of the solubility ina developing solution.

The polysiloxane to be used in the present invention can be synthesizedby hydrolyzing and partially condensing a monomer, such as theabove-mentioned organosilane, or an oligomer. The term “partialcondensation” as used herein refers to a procedure by which several ofSi—OH groups can remain in the polysiloxane, rather than condensing allof Si—OH groups in a hydrolysis product. The hydrolysis and the partialcondensation can be carried out employing the conventional methods. Forexample, a method can be mentioned, in which a solvent, water andoptionally a catalyst are added to an organosilane mixture and theresultant solution is stirring under heating at 50 to 150° C. for about0.5 to 100 hours. If necessary, a hydrolysis by-product (an alcohol suchas methanol) or a condensation by-product (water) may be distilled awayby distillation during the stirring.

The catalyst is not particularly limited, and an acid catalyst and abasic catalyst are preferably used. Specific examples of the acidcatalyst include hydrochloric acid, nitric acid, sulfuric acid,hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid,formic acid, a polyhydric carboxylic acid, an anhydride of any one ofthese acids, and an ion exchange resin. Specific examples of the basiccatalyst include triethylamine, tripropylamine, tributylamine,tripentylamine, trihexylamine, triheptylamine, trioctylamine,diethylamine, triethanolamine, diethanolamine, sodium hydroxide,potassium hydroxide, an alkoxysilane having an amino group, and an ionexchange resin.

From the viewpoint of the storage stability of the photosensitive resincomposition, it is preferred that the catalyst is not contained in apolysiloxane solution after the hydrolysis and the partial condensation,and the removal of the catalyst may be carried out as required. Themethod for the removal is not particularly limited, and is preferablywashing with water and/or a treatment with an ion exchange resin fromthe viewpoint of the easiness of operation and the removability of thecatalyst. Washing with water is a method in which the polysiloxanesolution is diluted with a proper hydrophobic solvent and is then washedwith water several times to produce an organic layer, and the organiclayer is concentrated with an evaporator or the like. A treatment withan ion exchange resin is a method in which the polysiloxane solution isbrought into contact with a proper ion exchange resin.

The resin composition according to the present invention contains (A3) aphenolic resin and/or a polyhydroxystyrene resin. It is preferred for aninsulating layer or a planarization film in an organic EL display toabsorb light having a wavelength of 350 to 460 nm, including ultravioletlight and visible light in a short wavelength range, which is believedto be greatly involved in the occurrence of deterioration ormalfunctions of the device or the development of a leakage current inthe device caused by the penetration of light into TFTs for driving thedevice. For the formation of an insulating layer or a planarization filmhaving the effect, it is considered to use a resin compositioncontaining a compound having the maximum absorption wavelength thereofat 350 to 460 nm, for example. When merely a resin compositioncontaining a compound having the maximum absorption wavelength thereofat 350 to 460 nm is used, however, the absorption of the light by theresin composition overlaps the absorption of g line (436 nm), h line(405 nm) and i line (365 nm) which correspond to the exposing lightwavelengths of a high-pressure mercury lamp. Therefore, it is difficultto penetrate the light to the bottom of the resin film during theexposure of the resin film to light to sensitize the resin film. Incontrast, when (A3) the phenolic resin and/or the polyhydroxystyreneresin according to the present invention is used, it becomes possible topenetrate light having a wavelength of the exposing light in aphotosensitive resin film that is not subjected to a heat treatment yet,and it becomes possible to cause a thermal oxidation reaction by theaction of oxygen present in air during a heat treatment to develop acolor and greatly absorb particularly light having a wavelength of 350to 400 nm, including ultraviolet light and visible light in a shortwavelength range, in a heat-resistant film that has been subjected tothe heat treatment after the exposure to the light. By using theheat-resistant resin film as an insulating layer or a planarization filmin a display device, it becomes possible to prevent the occurrence ofdeterioration or malfunctions of the device or the development of aleakage current in the device which is caused as the result of thepenetration of light into TFTs for driving the device.

Specific examples of the phenolic resin that can be used in the presentinvention include a novolac resin and a resol resin. The phenolic resincan be produced by polycondensing a single type of phenol compound or amixture of two or more types of phenol compounds with an aldehyde suchas formalin.

Examples of the phenols constituting the novolak resin and the resoleresin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol,2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol,3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol,2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol,methylenebisphenol, methylenebis-p-cresol, resorcinol, catechol,2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol,p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol,p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol,2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, a-naphthol, andβ-naphthol, and these phenols may be used singly, or a mixture of two ormore of them may be used.

Specific examples of the aldehyde include formalin, paraformaldehyde,acetaldehyde, benzaldehyde, hydroxybenzaldehyde and chloroacetaldehyde.These aldehydes may be used singly, or a mixture of two or more of themmay be used.

The phenolic resin to be used in the present invention may be one havinga structure in which each of 1 to 4 of hydrogen atoms added to anaromatic ring is substituted by an alkyl group having 1 to 20 carbonatoms, a fluoroalkyl group, an alkoxyl group, an alkoxymethyl group, amethylol group, an ester group, a nitro group, a cyano group, a fluorineatom or a chlorine atom.

The preferred weight average molecular weight of the phenolic resin tobe used in the present invention is 2,000 to 50,000, preferably 3,000 to30,000, as determined in terms of polystyrene by employing gelpermeation chromatography (GPC). When the molecular weight is 2,000 ormore, the form of a pattern, resolution, developability and heatresistance become excellent. When the molecular weight is 50,000 orless, sufficient sensitivity can be secured.

Specific examples of the polyhydroxystyrene resin that can be used inthe present invention include: a polymer or a copolymer which isproduced by polymerizing an aromatic vinyl compound having a phenolichydroxyl group, such as p-hydroxystyrene, m-hydroxystyrene,o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol ando-isopropenylphenol, singly or polymerizing two or more of the aromaticvinyl compounds by a known method; and a polymer or copolymer which isproduced by an addition reaction for adding an alkoxy group to a part ofa polymer or copolymer, which is produced by polymerizing an aromaticvinyl compound, such as styrene, o-methylstyrene, m-methylstyrene andp-methylstyrene, singly or polymerizing two or more of the aromaticvinyl compounds by a conventional known method, by a conventional knownmethod.

The aromatic vinyl compound having a phenolic hydroxyl group that can beused preferably is p-hydroxystyrene and/or m-hydroxystyrene, and styreneis used preferably as the aromatic vinyl compound.

The polyhydroxystyrene resin to be used in the present invention mayhave a structure in which each of 1 to 4 of hydrogen atoms added to thearomatic ring is substituted by an alkyl group having 1 to 20 carbonatoms, a fluoroalkyl group, an alkoxyl group, an alkoxymethyl group, amethylol group, an ester group, a nitro group, a cyano group, a fluorineatom or a chlorine atom.

The preferred weight average molecular weight of the polyhydroxystyreneresin to be used in the present invention is preferably 3,000 to 60,000,more preferably 3,000 to 25,000, as determined in terms of polystyreneby employing gel permeation chromatography (GPC). When the molecularweight is 3,000 or more, the form of a pattern, resolution,developability and heat resistance become excellent. When the molecularweight is 60,000 or less, sufficient sensitivity can be secured.

In the present invention, the content of the component (A3) is 5 to 50parts by weight, particularly preferably 10 to 40 parts by weight,relative to 100 parts by weight of (A1) the polyimide, thepolybenzoxazole, the polyimide precursor or the polybenzoxazoleprecursor or (A2) the resin having such a backbone structure that twocyclic structures are bonded to a cyclic-structure-constitutingquaternary carbon atom. When the content of the component (A3) is 5parts by weight or more, it becomes possible to decrease a transmittanceof a cured film to light having a wavelength within an ultraviolet tovisible light wavelength range. When the content is 50 parts by weightor less, the heat resistance or strength of the cured film can beretained and the water absorption rate of the cured film and theformation of scums during development can be reduced.

In the present invention, the term “heat treatment” refers to aprocedure of heating at a temperature within the range from 200 to 350°C., more preferably 230° C. or higher. When the heat treatment iscarried out at 230° C. or higher, the heat resistance or strength of thecured film can be increased and a thermal oxidation reaction can proceedto decrease the transmittance.

The resin composition according to the present invention contains (B) athermally color-developing compound. The thermally color-developingcompound (B) can produce a color upon a heat treatment and has anabsorption maximum at a wavelength of 350 to 700 nm inclusive. Morepreferably, the thermally color-developing compound (B) can produce acolor upon a heat treatment and has an absorption maximum at awavelength of 350 to 500 nm inclusive. When the component (A3) and thethermally color-developing compound (B) are used, it becomes possible togreatly decrease the transmittance to light having a wavelength of 350to 460 nm after a heat treatment.

The component (B) to be used in the present invention is preferably athermally color-developing compound which can produce a color at atemperature higher than 120° C., and is more preferably a thermallycolor-developing compound which can produce a color at a temperaturehigher than 180° C. The heat resistance under high-temperatureconditions becomes superior with the increase in the color-developingtemperature of the thermally color-developing compound, and thethermally color-developing compound rarely undergoes discoloration uponthe irradiation with ultraviolet light or visible light for a longperiod and therefore has excellent light resistance.

The component (B) to be used in the present invention may be a commonheat-sensitive dye or a common pressure-sensitive dye, or may be anothercompound. Examples of the thermally color-developing compound include:one which can produce a color as the result of the change in thechemical structure or the state of electric charge by the action of anacidic group co-existing in the system during the heat treatment; andone which can produce a color as the result of the occurrence of athermal oxidation reaction by the action of oxygen present in air.Examples of the backbone structure of the thermally color-developingcompound include a triarylmethane backbone, a diarylmethane backbone, afluoran backbone, a bislactone backbone, a phthalide backbone, axanthene backbone, a rhodamine lactam backbone, a fluorene backbone, aphenothiazine backbone, a phenoxazine backbone and a spiropyranbackbone. Specific examples of the (B) component include4,4′,4″-tris(dimethylamino)triphenylmethane,4,4′,4″-tris(diethylamino)-2,2′,2″-trimethyltriphenylmethane,2,4′,4″-methylidenetrisphenol, 4,4′,4″-methylidenetrisphenol,4,4′-[(4-hydroxyphenyl)methylene]bis(benzenamine),4,4′-[(4-aminophenyl)methylene]bisphenol,4,4′-[(4-aminophenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4-[bis(4-hydroxyphenyl)methyl]-2-methoxyphenol,4,4′-[(2-hydroxyphenyl)methylene]bis[2-methylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-methylphenol],4-[bis(4-hydroxyphenyl)methyl]-2-ethoxyphenol,4,4-[(3-hydroxyphenyl)methylene]bis[2,6-dimethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2,6-dimethyl phenol],2,2′-[(2-hydroxyphenyl)methylene]bis[2,3,5-trimethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(3-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(3-methoxy-4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-methylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2,6-dimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4-[bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)methyl]-1,2-benzenediol,4,4′,4″,4′″-(1,2-ethanediylidene)tetrakisphenol,4,4′,4″,4′″-(1,2-ethanediylidene)tetrakis[2-methylphenol],4,4′,4″,4′″-(1,2-ethanediylidene)tetrakis[2,6-dimethylphenol],4,4′,4″,4′″-(1,4-phenylenemethylidene)tetrakisphenol,4,4′,4″,4′″-(1,4-phenylenemethylidene)tetrakis(2,6-dimethylphenol),4,4′-[(2-hydroxyphenyl)methylene]bis[3-methylphenol],2,2′-[(3-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2,5-dimethylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[3,5-dimethyl phenol],2,2′-[(3-hydroxy-4-methoxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-methylethylphenol],4,4′-[(3-hydroxyphenyl)methylene]bis[2-methylethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-methylethylphenol],2,2′-[(3-hydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2-(methylethyl)phenol],4,4′-[(3-hydroxy-4-methoxyphenyl)methylene]bis[2-(methylethyl)phenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(3-hydroxy-4-methoxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2,3,6-trimethylphenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2-(1,1-dimethylethyl)-5-methylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(3-hydroxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(3-hydroxy-4-methoxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-(1,1-dimethylethyl)-6-methylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′,4″-methylidenetris[2-cyclohexyl-5-methylphenol],2,2′-[(3,4-dihydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(3,4-dihydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-cyclohexylphenol],3,3′-[(2-hydroxyphenyl)methylene]bis[5-methylbenzene-1,2-diol],4,4′-[4-[[bis(4-hydroxy-2,5-dimethylphenyl)methyl]phenyl]methylene]bis[1,3-benzenediol],4,4′-methylenebis[2-[di(4-hydroxy-3-methylphenyl)]methyl]phenol,4,4′-methylenebis[2-[di(4-hydroxy-2,5-dimethylphenyl)]methyl]phenol,4,4′-methylenebis[2-[di(4-hydroxy-3,5-dimethylphenyl)methyl]phenol,4,4′-methylenebis[2-[di(3-cyclohexyl-4-hydroxy-6-methylphenyl)]methyl]phenol,4,4′-(3,5-dimethyl-4-hydroxyphenylmethylene)-bis(2,6-dimethylphenol),3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide,3,6-bis(dimethylamino)fluoran-γ-(4′-nitro)-aminolactam,2-(2-chloroanilino)-6-diethylaminofluoran,2-(2-chloroanilino)-6-dibutylaminofluoran,2-N,N-dibenzylamino-6-diethylaminofluoran,6-diethylamino-benzo[a]-fluoran,2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-bi(imidazole),1,3-dimethyl-6-diethylaminofluoran,2-anilino-3-methyl-6-dibutylaminofluoran,3,7-bis(dimethylamino)-10-benzoylphenothiazine,3-diethylamino-6-chloro-7-(β-ethoxyethylamino)fluoran,3-diethylamine-6-methyl-7-anilinofluoran,3-triethylamino-6-methyl-7-anilinofluoran, and3-cyclohexylamino-6-methyl-7-anilinofluoran.

Among these compounds, a hydroxy-group-containing compound having atriarylmethane backbone represented by general formula (2) or (3) ispreferred.

R¹⁰ to R²⁵ may be the same as or different from one another, andindependently represent a monovalent group selected from a hydrogenatom, a hydrocarbon group having 1 to 12 carbon atoms, a cyclicaliphatic group having 3 to 8 carbon atoms, a hydrocarbon group having 6to 15 carbon atoms and having an aromatic ring and an alkoxy grouphaving 1 to 4 carbon atoms. r represents 0 or 1, preferably 0. srepresents an integer of 0 to 3, preferably 1. e1 to e23 independentlyrepresent an integer of 0 to 4, wherein e1+e2+e3>0 ande10+e11+e12+e13>0.

Specifically, hydroxyl group-containing compounds having atriarylmethane skeleton, such as the following compounds, areparticularly preferred due to their high thermal color developingtemperature and excellent high heat resistance:2,4′,4″-methylidenetrisphenol, 4,4′,4″-methylidenetrisphenol,4,4′-[(4-hydroxyphenyl)methylene]bis(benzeneamine),4,4′-[(4-aminophenyl)methylene]bisphenol,4,4′-[(4-aminophenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4-[bis(4-hydroxyphenyl)methyl]-2-methoxyphenol,4,4′-[(2-hydroxyphenyl)methylene]bis[2-methylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-methylphenol],4-[bis(4-hydroxyphenyl)methyl]-2-ethoxyphenol,4,4′-[(4-hydroxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2,6-dimethyl phenol],2,2′-[(2-hydroxyphenyl)methylene]bis[2,3,5-trimethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-cyclohexyl 5-methylphenol],4,4′-[(3-methoxy-4-hydroxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-methylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2,6-dimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2,3,6-trimethylphenol],4-[bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)methyl]-1,2-benzenediol,4,4′,4″,4′″-(1,2-ethanediylidene)tetrakisphenol,4,4′,4″,4′″-(1,2-ethanediylidene)tetrakis[2-methylphenol],4,4′,4″,4′″-(1,2-ethanediylidene)tetrakis[2,6-dimethylphenol],4,4′,4″,4′″-(1,4-phenylenedimethylidene)tetrakisphenol,4,4′,4″,4′″-(1,4-phenylenedimethylidene)tetrakis(2,6-dimethylphenol),4,4′-[(2-hydroxyphenyl)methylene]bis[3-methylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2,5-dimethylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-methylethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-methylethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2-(methylethyl)phenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[3,5,6-trimethylphenol],2,2′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2,3,6-trimethylphenol],4,4′-[(4-hydroxy-3-methoxyphenyl)methylene]bis[2-(1,1-dimethylethyl)-5-methylphenol],4,4′-[(2-hydroxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(2-hydroxy-3-methoxyphenyl)methylene]bis[2-cyclohexylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-(1,1-dimethylethyl)-6-methylphenol],4,4′-[(4-hydroxy-3-ethoxyphenyl)methylene]bis[2-cyclohexyl-5-methylphenol],4,4′,4″-methylidenetris[2-cyclohexyl-5-methylphenol],2,2′-[(3,4-dihydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-(methylethyl)phenol],2,2′-[(3,4-dihydroxyphenyl)methylene]bis[3,5,6-trimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2-cyclohexylphenol],3,3′-[(2-hydroxyphenyl)methylene]bis[5-methylbenzene-1,2-diol],4,4′-[4-[[bis(4-hydroxy-2,5-dimethylphenyl)methyl]phenyl]methylene]bis[1,3-benzenediol],4,4′-methylenebis[2-[di(4-hydroxy-3-methylphenyl)]methyl]phenol,4,4′-methylenebis[2-[di(4-hydroxy-2,5-dimethylphenyl)]methyl]phenol,4,4′-methylenebis[2-[di(4-hydroxy-3,5-dimethylphenyl)methyl]phenol,4,4′-methylenebis[2-[di(3-cyclohexyl-4-hydroxy-6-methylphenyl)]methyl]phenol,and4,4′-(3,5-dimethyl-4-hydroxyphenylmethylene)-bis(2,6-dimethylphenol).These compounds may be used singly, or a mixture of two or more of themmay be used. Alternatively, the hydroxy-group-containing compound havinga triarylmethane backbone may be used in the form of a quinone diazidecompound which is produced by bonding naphthoquinone diazide sulfonicacid to the hydroxy-group-containing compound having a triarylmethanebackbone via an ester bond.

The amount of the thermally color-developing compound (B) to be used inthe present invention is preferably 5 to 80 parts by weight,particularly preferably 10 to 60 parts by weight, relative to 100 partsby weight of (A1) the polyimide, the polybenzoxazole, the polyimideprecursor or the polybenzoxazole precursor or (A2) the resin having sucha backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom. When the amount ofthe component (B) to be used is 5 parts by weight or more, it becomespossible to decrease the transmittance of a cured film to light having awavelength within an ultraviolet to visible light range. When the amountis 80 parts by weight or less, it becomes possible to maintain heatresistance or strength of the cured film and decrease the waterabsorption ratio of the cured film.

The resin composition according to the present invention contains (C) aphoto-acid generator. Specific examples of the photo-acid generator (C)include a quinone diazide compound, a sulfonium salt, a phosphoniumsalt, a diazonium salt and an iodonium salt.

Examples of the quinone diazide compound include: a compound produced bybonding quinone diazide sulfonic acid to a polyhydroxyl compound or apolyamino compound via an ester bond; a compound produced by bondingquinone diazide sulfonic acid to a polyhydroxyl compound via asulfoneamide bond; and a compound produced by bonding quinone diazidesulfonic acid to a polyhydroxyl polyamino compound via an ester bondand/or a sulfoneamide bond. In these compounds, it is preferred that 50mol % or more of all of functional groups in the polyhydroxyl compoundor the polyamino compound is substituted by quinone diazide. When aquinone diazide compound in which 50 mol % or more is substituted isused, the affinity of the quinone diazide compound for an aqueousalkaline solution is reduced, the solubility of an unexposed part of theresin composition in an aqueous alkaline solution is greatly reduced,and the quinone diazide sulfonyl group is converted to an indenecarboxylic acid upon exposure to light to achieve a high dissolutionrate of an exposed part of the resin composition in an aqueous alkalinesolution, resulting in the increase in the ratio of the dissolution rateof the exposed part of the composition to the dissolution rate of theunexposed part of the composition. As a result, a pattern with a highdegree of resolution can be obtained. By using the quinone diazidecompound, it becomes possible to produce a positive-workingphotosensitivity resin composition which can be photosensitized with iline (365 nm), h line (405 nm) and g line (436 nm) of a conventionalmercury lamp. These photo-acid generators may be used singly, or two ormore of them may be used in combination. In either case, ahigh-sensitivity photosensitive resin composition can be produced.

In the present invention, either of a quinone diazide having a5-naphthoquinone diazide sulfonyl group or a quinone diazide having a4-naphthoquinone diazide sulfonyl group can be used preferably. Theabsorption of a naphthoquinone diazide sulfonyl ester compound extendsto a g line range of a mercury lamp, and is therefore suitable for theexposure to g line and the exposure to light within the whole wavelengthrange. A 4-naphthoquinone diazide sulfonyl ester compound has anabsorption in an i line range of a mercury lamp, and is thereforesuitable for the exposure to i line. In the present invention, it ispreferred to select a 4-naphthoquinone diazide sulfonyl ester compoundor a 5-naphthoquinone diazide sulfonyl ester compound depending on thewavelength to be exposed. It is also possible to produce anaphthoquinone diazide sulfonyl ester compound having both a4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazidesulfonyl group in the molecule thereof, or it is also possible to useboth a 4-naphthoquinone diazide sulfonyl ester compound and a5-naphthoquinone diazide sulfonyl ester compound in combination.

The molecular weight of the quinone diazide compound is preferably 300or more, more preferably 350 or more, and is preferably 3000 or less,more preferably 1500 or less, from the viewpoint of the heat resistance,mechanical properties and bonding properties of a film produced by aheat treatment.

The content of the quinone diazide compound is preferably 1 part byweight or more, more preferably 3 parts by weight or more, and ispreferably 100 parts by weight or less, more preferably 80 parts byweight or less, relative to 100 parts by weight of (A1) the polyimide,the polybenzoxazole, the polyimide precursor or the polybenzoxazoleprecursor or (A2) the resin having such a backbone structure that twocyclic structures are bonded to a cyclic-structure-constitutingquaternary carbon atom. When the content is 1 to 100 parts by weight, itbecomes possible to impart photosensitiveness to a film produced after aheat treatment while maintaining the heat resistance, chemicalresistance and mechanical properties of the film.

In the case where the quinone diazide compound is contained as thethermally color-developing compound (B), the compound can also act asthe photo-acid generator (C). In this case, the content of the quinonediazide compound is preferably 5 parts by weight or more, morepreferably 10 parts by weight or more, and is preferably 100 parts byweight or less, more preferably 80 parts by weight or less, relative to100 parts by weight of (A1) the polyimide, the polybenzoxazole, thepolyimide precursor or the polybenzoxazole precursor or (A2) the resinhaving such a backbone structure that two cyclic structures are bondedto a cyclic-structure-constituting quaternary carbon atom. When thecontent is 5 to 100 parts by weight, it becomes possible to decrease thetransmittance of a film produced after a heat treatment and impartphotosensitiveness to the film while maintaining the heat resistance,chemical resistance and mechanical properties of the film.

Among these photo-acid generators, a sulfonium salt, a phosphonium saltand a diazonium salt are preferred, because an acid component generatedupon the exposure to light can be stabilized appropriately.Particularly, a sulfonium salt is preferred.

The content of the sulfonium salt, the phosphonium salt or the diazoniumsalt is preferably 0.5 to 20 parts by weight relative to 100 parts byweight of (A1) the polyimide, the polybenzoxazole, the polyimideprecursor or the polybenzoxazole precursor or (A2) the resin having sucha backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, from the viewpointof increasing sensitivity. In addition, a sensitizer or the like may becontained, if necessary.

The resin composition according to the present invention contains (D) asolvent. Specific examples of the solvent to be used in the presentinvention include: a polar aprotic solvent, such asN-methyl-2-pyrrolidone, gamma-butyrolactone, N,N-dimethylformamide,N,N-dimethylacetamide and dimethyl sulfoxide; an ether, such astetrahydrofuran, dioxane and propylene glycol monomethyl ether; aketone, such as acetone, methyl ethyl ketone, diisobutyl ketone anddiacetone alcohol; an ester, such as ethyl acetate, propylene glycolmonomethyl ether acetate and ethyl lactate; and an aromatic hydrocarbon,such as toluene and xylene. These solvents may be used singly, or two ormore of them may be used in combination.

The content of the solvent to be used in the present invention ispreferably 50 parts by weight or more, more preferably 100 parts byweight or more, and is preferably 2000 parts by weight or less, morepreferably 1500 parts by weight or less, relative to 100 parts by weightof (A1) the polyimide, the polybenzoxazole, the polyimide precursor orthe polybenzoxazole precursor or (A2) the resin having such a backbonestructure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom.

The resin composition according to the present invention preferablycontains (E) a dye and/or a pigment. As this compound, a dye and/or anorganic pigment can be used preferably. At least one type of thecomponent (E) may be contained. For example, a method in which one typeof dye or organic pigment is used, a method in which at least two typesof dyes or organic pigments are used as a mixture, a method in which atleast one type of dye and at least one type of organic pigment are usedin combination, and the like can be mentioned. In the present invention,a dye and/or a pigment each having an absorption maximum at 400 to 750nm is preferably selected.

The component (E) to be used in the resin composition according to thepresent invention preferably contains (E1) a dye and/or a pigment eachhaving an absorption maximum at a wavelength of 400 nm or more and lessthan 490 nm.

The dye to be used as the component (E1) in the present invention ispreferably: a dye which is soluble in an organic solvent that candissolve (A1) the polyimide, the polybenzoxazole, the polyimideprecursor or the polybenzoxazole precursor or (A2) the resin having sucha backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, and which iscompatible with the resin; or a dye having high heat resistance and highlight resistance, from the viewpoint of storage stability anddiscoloration upon curing or irradiation with light. The component (E1)has an absorption maximum at a wavelength of 400 nm or more and lessthan 490 nm, and specific examples thereof include a yellow dye and anorange dye. The type of the dye includes an oil-soluble dye, adispersible dye, a reactive dye, an acidic dye, a direct dye and thelike.

Examples of the backbone structure of the dye include, but not limitedto, those of an anthraquinone-type, an azo-type, a phthalocyanine-type,a methine-type, an oxazine-type, a quinoline-type, atriarylmethane-type, and a xanthene-type. Among these backbonestructures, backbone structures of an anthraquinone-type, an azo-type, amethine-type, a triarylmethane-type and a xanthene-type are preferred,from the viewpoint of the solubility in an organic solvent and heatresistance. These dyes may be used singly or may be used in the form ofa metal-containing complex salt. Specific examples thereof include, butare not limited to, Sumilan and Lanyl dyes (manufactured by SumitomoChemical Co., Ltd.); Orasol, Oracet, Filamid, and Irgasperse dyes(manufactured by Ciba Specialty Chemicals Inc.); Zapon, Neozapon,Neptune, and Acidol dyes (manufactured by BASF Corporation); Kayaset andKayakalan dyes (manufactured by Nippon Kayaku Co., Ltd.); Valifastcolors dye (manufactured by Orient Chemical Industries, Ltd.); Savinyl,Sandoplast, Polysynthren, and Lanasyn dyes (manufactured by ClariantJapan Co., Ltd.); Aizen Spilon dye (manufactured by Hodogaya ChemicalCo., Ltd.); functional dye (manufactured by Yamada Chemical Co., Ltd.);and Plast Color dye, and Oil Color dye (manufactured by Arimoto ChemicalCo., Ltd.). These dyes may be used singly, or a mixture of two or moreof them may be used.

The pigment to be used as the component (E1) in the present invention ispreferably a pigment having high heat resistance and light resistance,from the viewpoint of discoloration during curing or irradiation withlight.

Specific examples of the organic pigment to be used are mentioned interms of color index (CI) numbers as follows. Specific examples of theyellow pigment include pigment yellow 83, 117, 129, 138, 139, 150 and180. Specific examples of the orange pigment include pigment orange 38,43, 64, 71 and 72. A pigment other than the above-mentioned pigments mayalso be used.

The content of the component (E1) to be used in the present invention ispreferably 0.1 to 300 parts by weight, more preferably 0.2 to 200 partsby weight, particularly preferably 1 to 200 parts by weight, relative to100 parts by weight of (A1) the polyimide, the polybenzoxazole, thepolyimide precursor or the polybenzoxazole precursor or (A2) the resinhaving such a backbone structure that two cyclic structures are bondedto a cyclic-structure-constituting quaternary carbon atom. When thecontent of the component (E1) is 0.1 part by weight or more, it becomespossible to absorb light having a wavelength corresponding to thepigment. When the content is 300 parts by weight or less, it becomespossible to absorb light having a wavelength corresponding to thepigment while maintaining the adhesion strength between a photosensitivecolor resin film and a substrate and also maintaining the heatresistance and mechanical properties of a film after a heat treatment.

In the present invention, the organic pigment to be used as thecomponent (E1) may be subjected to a surface treatment, such as a rosintreatment, an acidic group treatment and a basic group treatment, ifnecessary. The organic pigment may also be used together with adispersant optionally. Examples of the dispersant include a cationicsurfactant, an anionic surfactant, a nonionic surfactant, an amphotericsurfactant, a silicone-type surfactant and a fluorine-containingsurfactant.

The component (E) to be used in the resin composition according to thepresent invention preferably contains (E2) a dye and/or a pigment eachhaving an absorption maximum at a wavelength of 490 nm or more and lessthan 580 nm.

The dye to be used as the component (E2) in the present invention ispreferably: a dye which is soluble in an organic solvent that candissolve (A1) the polyimide, the polybenzoxazole, the polyimideprecursor or the polybenzoxazole precursor or (A2) the resin having sucha backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, and which iscompatible with the resin; or a dye having high heat resistance and highlight resistance, from the viewpoint of storage stability anddiscoloration upon curing or irradiation with light. The component (E2)has an absorption maximum at a wavelength of 490 nm or more and lessthan 580 nm, and examples thereof include a red dye and a violet dye.

The type of the dye includes an oil-soluble dye, a dispersible dye, areactive dye, an acidic dye, a direct dye and the like.

Examples of the backbone structure of the dye include, but not limitedto, those of an anthraquinone-type, an azo-type, a phthalocyanine-type,a methine-type, an oxazine-type, a quinoline-type, atriarylmethane-type, and a xanthene-type. Among these backbonestructures, backbone structures of an anthraquinone-type, an azo-type, amethine-type, a triarylmethane-type and a xanthene-type are preferred,from the viewpoint of the solubility in an organic solvent and heatresistance. These dyes may be used singly or may be used in the form ofa metal-containing complex salt. Specific examples thereof include, butare not limited to, Sumilan and Lanyl dyes (manufactured by SumitomoChemical Co., Ltd.); Orasol, Oracet, Filamid, and Irgasperse dyes(manufactured by Ciba Specialty Chemicals Inc.); Zapon, Neozapon,Neptune, and Acidol dyes (manufactured by BASF Corporation); Kayaset andKayakalan dyes (manufactured by Nippon Kayaku Co., Ltd.); Valifastcolors dye (manufactured by Orient Chemical Industries, Ltd.); Savinyl,Sandoplast, Polysynthren, and Lanasyn dyes (manufactured by ClariantJapan Co., Ltd.); Aizen Spilon dye (manufactured by Hodogaya ChemicalCo., Ltd.); functional dye (manufactured by Yamada Chemical Co., Ltd.);and Plast Color dye, and Oil Color dye (manufactured by Arimoto ChemicalCo., Ltd.). These dyes may be used singly, or a mixture of two or moreof them may be used.

The pigment to be used as the component (E2) in the present invention ispreferably a pigment having high heat resistance and light resistance,from the viewpoint of discoloration during curing or irradiation withlight.

Specific examples of the organic pigment to be used are mentioned interms of color index (CI) numbers as follows. Specific examples of thered pigment include pigment red 48:1, 122, 168, 177, 202, 206, 207, 209,224, 242 and 254. Specific examples of the violet pigment includepigment violet 19, 23, 29, 32, 33, 36, 37 and 38. A pigment other thanthe above-mentioned pigments may also be used.

The content of the component (E2) to be used in the present invention ispreferably 0.1 to 300 parts by weight, more preferably 0.2 to 200 partsby weight, particularly preferably 1 to 200 parts by weight, relative to100 parts by weight of (A1) the polyimide, the polybenzoxazole, thepolyimide precursor or the polybenzoxazole precursor or (A2) the resinhaving such a backbone structure that two cyclic structures are bondedto a cyclic-structure-constituting quaternary carbon atom. When thecontent of the component (E2) is 0.1 part by weight or more, it becomespossible to absorb light having a wavelength corresponding to thepigment. When the content is 300 parts by weight or less, it becomespossible to absorb light having a wavelength corresponding to thepigment while maintaining the adhesion strength between a photosensitivecolor resin film and a substrate and the heat resistance and mechanicalproperties of a film after a heat treatment.

In the present invention, the organic pigment to be used as thecomponent (E2) may be subjected to a surface treatment, such as a rosintreatment, an acidic group treatment and a basic group treatment, ifnecessary. The organic pigment may also be used together with adispersant, if necessary. Examples of the dispersant include a cationicsurfactant, an anionic surfactant, a nonionic surfactant, an amphotericsurfactant, a silicone-type surfactant and a fluorine-containingsurfactant.

The component (E) to be used in the resin composition according to thepresent invention preferably contains (E3) a dye and/or a pigment havingan absorption maximum at a wavelength of 580 nm or more and less than800 nm.

The dye to be used as the component (E3) in the present invention ispreferably a dye which is soluble in an organic solvent that candissolve (A1) the polyimide, the polybenzoxazole, the polyimideprecursor or the polybenzoxazole precursor or (A2) the resin having sucha backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, and which iscompatible with the resin, or a dye having high heat resistance and highlight resistance, from the viewpoint of storage stability anddiscoloration upon curing or irradiation with light. The component (E3)has an absorption maximum at a wavelength of 580 nm or more and lessthan 800 nm, and examples thereof include a blue dye and a green dye.

The type of the dye includes an oil-soluble dye, a dispersible dye, areactive dye, an acidic dye, a direct dye and the like.

Examples of the backbone structure of the dye include, but not limitedto, those of an anthraquinone-type, an azo-type, a phthalocyanine-type,a methine-type, an oxazine-type, a quinoline-type, atriarylmethane-type, and a xanthene-type. Among these backbonestructures, backbone structures of an anthraquinone-type, an azo-type, amethine-type, a triarylmethane-type and a xanthene-type are preferred,from the viewpoint of the solubility in an organic solvent and heatresistance. These dyes may be used singly or may be used in the form ofa metal-containing complex salt. Specific examples thereof include, butare not limited to, Sumilan and Lanyl dyes (manufactured by SumitomoChemical Co., Ltd.); Orasol, Oracet, Filamid, and Irgasperse dyes(manufactured by Ciba Specialty Chemicals Inc.); Zapon, Neozapon,Neptune, and Acidol dyes (manufactured by BASF Corporation); Kayaset andKayakalan dyes (manufactured by Nippon Kayaku Co., Ltd.); Valifastcolors dye (manufactured by Orient Chemical Industries, Ltd.); Savinyl,Sandoplast, Polysynthren, and Lanasyn dyes (manufactured by ClariantJapan Co., Ltd.); Aizen Spilon dye (manufactured by Hodogaya ChemicalCo., Ltd.); functional dye (manufactured by Yamada Chemical Co., Ltd.);and Plast Color dye, and Oil Color dye (manufactured by Arimoto ChemicalCo., Ltd.). These dyes may be used singly, or a mixture of two or moreof them may be used.

The pigment to be used as the component (E3) in the present invention ispreferably a pigment having high heat resistance and light resistance,from the viewpoint of discoloration during curing or irradiation withlight.

Specific examples of the organic pigment to be used are mentioned interms of color index (CI) numbers as follows. Specific examples of theblue pigment include pigment blue 15 (e.g., 15:3, 15:4, 15:6), 21, 22,60 and 64. Specific examples of the green pigment include pigment green7, 10, 36, 47 and 58. A pigment other than the above-mentioned pigmentsmay also be used.

The content of the component (E3) to be used in the present invention ispreferably 0.1 to 300 parts by weight, more preferably 0.2 to 200 partsby weight, particularly preferably 1 to 200 parts by weight, relative to100 parts by weight of (A1) the polyimide, the polybenzoxazole, thepolyimide precursor or the polybenzoxazole precursor or (A2) the resinhaving such a backbone structure that two cyclic structures are bondedto a cyclic-structure-constituting quaternary carbon atom. When thecontent of the component (E3) is 0.1 part by weight or more, it becomespossible to absorb light having a wavelength corresponding to thepigment. When the content is 300 parts by weight or less, it becomespossible to absorb light having a wavelength corresponding to thepigment while maintaining the adhesion strength between a photosensitivecolor resin film and a substrate and the heat resistance and mechanicalproperties of a film after a heat treatment.

In the present invention, the organic pigment to be used as thecomponent (E3) may be subjected to a surface treatment, such as a rosintreatment, an acidic group treatment and a basic group treatment, ifnecessary. The organic pigment may also be used together with adispersant, if necessary. Examples of the dispersant include a cationicsurfactant, an anionic surfactant, a nonionic surfactant, an amphotericsurfactant, a silicone-type surfactant and a fluorine-containingsurfactant.

In the present invention, the film can be blackened by additionallyusing the components (E1), (E2) and (E3). The degree of blackening canbe expressed by an optical density (an OD value), and the OD value ispreferably 0.15 or more, more preferably 0.4 or more, still morepreferably 1.0 or more.

The resin composition according to the present invention mayadditionally contain (F) a compound having 3 to 6 thermallycrosslinkable groups per molecule. When the component (F) is contained,it becomes possible to impart positive-working photosensitivity andimprove the chemical resistance of the heat-resistant resin film.

As the component (F), a compound represented by general formula (4) or acompound having a structure represented by general formula (5) ispreferred.

In general formula (4) above, R²⁶ represents a bivalent to tetravalentlinking group. R²⁷ represents Cl, Br, I, F, a monovalent hydrocarbongroup having 1 to 20 carbon atoms, a group having such a structure that—CH₂— in a monovalent hydrocarbon group having 1 to 20 carbon atoms issubstituted by —CO—, —COO—, —NH—, —NHCO—, —O—, —S—, —SO₂—, —Si— or—Si(CH₃)₂—, or a group having such a structure that a hydrogen atom in amonovalent hydrocarbon group having 1 to 20 carbon atoms is substitutedby a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitrogroup, a cyano group, a fluorine atom, a chlorine atom or —COOR³¹. R³¹represents a hydrogen atom or an alkyl group having 1 to 20 carbonatoms. R²⁸ and R²⁹ independently represent CH₂OR³² that is a thermallycrosslinkable group. R³² represents a hydrogen atom or a monovalenthydrocarbon group having 1 to 6 carbon atoms. R³⁰ represents a hydrogenatom, a methyl group or an ethyl group. R³² is preferably a monovalenthydrocarbon group having 1 to 4 carbon atoms, because proper reactivitycan still remain and excellent storage stability can be achieved. In aphotosensitive resin composition containing a photo-acid generator andthe like, R³² is more preferably a methyl group or an ethyl group. trepresents an integer of 0 to 2, and u represents an integer of 2 to 4.The multiple R²⁷'s, R²⁸'s, R²⁹'s and R³⁰'s may be the same as ordifferent from one another. Specific examples of the linking group R²⁶are as follows.

In the formula, R³³ to R⁵³ independently represent a hydrogen atom, Cl,Br, I, F, a monovalent hydrocarbon group having 1 to 20 carbon atoms, agroup having such a structure that —CH₂— in a monovalent hydrocarbongroup having 1 to 20 carbon atoms is substituted by —CO—, —COO—, —NH—,—NHCO—, —O—, —S—, —SO₂—, —Si— or —Si(CH₃)₂—, or a group having such astructure that a hydrogen atom in a monovalent hydrocarbon group having1 to 20 carbon atoms is substituted by a fluoroalkyl group, a hydroxylgroup, an alkoxyl group, a nitro group, a cyano group, a fluorine atom,a chlorine atom, or —COOR⁵⁴. R⁵⁴ represents a hydrogen atom or an alkylgroup having 1 to 20 carbon atoms.

—N(CH₂OR⁵⁵)_(v)(H)_(w)  (5)

In general formula (5), R⁵⁵ represents a hydrogen atom or a monovalenthydrocarbon group having 1 to 6 carbon atoms. v represents 1 or 2, and wrepresents 0 or 1, wherein v+w is 1 or 2.

The purity of the compound having a structure represented by generalformula (4) is preferably 75% or more, more preferably 85% or more. Whenthe purity is 85% or more, it becomes possible to achieve excellentstorage stability, to perform the crosslinking reaction of the resincomposition satisfactorily to achieve excellent coloring propertiesafter curing, and to further decrease the transmittance of theheat-resistant resin film to light having a wavelength within a visiblelight range. In addition, it also becomes possible to reduce the numberof unreacted groups that act as water-absorbable groups, resulting inthe decrease in water absorbability of the resin composition. As themethod for producing a high-purity thermal crosslinking agent, methodssuch as recrystallization and distillation can be mentioned. The purityof the thermal crosslinking agent can be determined by a liquidchromatography method.

Preferred examples of the compound having a structure represented bygeneral formula (4) are as follows.

Preferred examples of the thermal crosslinking agent having a structurerepresented by general formula (5) are as follows.

In the present invention, an epoxy compound is also preferred as thecomponent (F). Examples of the epoxy compound include, but are notlimited to, TEPIC (registered trademark) S, TEPIC (registered trademark)G, and TEPIC (registered trademark) P (trade names, manufactured byNISSAN CHEMICAL INDUSTRIES, LTD.), DENACOL (registered trademark)EX-321L (trade name, manufactured by Nagase ChemteX Corporation),VG3101L (trade name, manufactured by Printec Co.), EPPN 502H and NC3000(trade names, manufactured by Nippon Kayaku Co., Ltd.), and EPICLON(registered trademark) N695 and HP-7200 (trade names, manufactured byDIC CORPORATION).

In the present invention, these components (F) may be used singly, ortwo or more of them may be used in combination.

The content of the component (F) is preferably 5 parts by weight ormore, more preferably 10 parts by weight or more, and is preferably 120parts by weight or less, more preferably 100 parts by weight or less,relative to 100 parts by weight of (A1) the polyimide, thepolybenzoxazole, the polyimide precursor or the polybenzoxazoleprecursor or (A2) the resin having such a backbone structure that twocyclic structures are bonded to a cyclic-structure-constitutingquaternary carbon atom. When the content is 5 to 120 parts by weightinclusive, the strength of the heat-resistant resin film is increasedand the storage stability of the resin composition becomes excellent.

The resin composition according to the present invention mayadditionally contain (G) a compound having a phenolic hydroxyl group.Because the compound can compensate alkali developability, it becomespossible to impart positive-working photosensitivity.

Examples of the compound having a phenolic hydroxyl group include, butare not limited to, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA,TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ,BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X,DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X,DML-EP, DML-POP, dimethylol-BisOC-P, DMLPFP, DML-PSBP, DML-MTrisPC,TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP,HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu ChemicalIndustry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP,BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (tradenames, manufactured by ASAHI YUKIZAI CORPORATION),2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol,2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methylgallate, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP(trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

In the present invention, the content of the component (G) is preferably3 to 50 parts by weight inclusive relative to 100 parts by weight of(A1) the polyimide, the polybenzoxazole, the polyimide precursor or thepolybenzoxazole precursor or (A2) the resin having such a backbonestructure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom.

The resin composition according to the present invention mayadditionally contain (H) a thermal acid generator. The thermal acidgenerator can generate an acid upon a heat treatment after developmentas mentioned below to accelerate the crosslinking reaction between (A1)the polyimide, the polybenzoxazole, the polyimide precursor or thepolybenzoxazole precursor or (A2) the resin having such a backbonestructure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom and the component(F) (i.e., the thermal crosslinking agent), and also accelerate thecyclization of an imide ring or an oxazole ring in (A1) the polyimideprecursor or the polybenzoxazole precursor. As a result, the chemicalresistance of the heat-resistant resin film can be improved and thethinning of the film can be prevented. The acid generated from thethermal acid generator is preferably a strong acid, and is preferably,for example, an arylsulfonic acid such as p-toluenesulfonic acid andbenzene sulfonic acid, and an alkylsulfonic acid such as methanesulfonicacid, ethanesulfonic acid and butanesulfonic acid. In the presentinvention, the thermal acid generator is preferably any one of aliphaticsulfonic acid compounds each represented by general formula (6) or (7).Two or more of these compounds may be contained.

In general formulae (6) and (7), R⁵⁶ to R⁵⁸ independently represent analkyl group having 1 to 10 carbon atoms or a monovalent aromatic grouphaving 7 to 12 carbon atoms. In the alkyl group and the aromatic group,at least one hydrogen atom may be substituted. Specific examples of thesubstituent include an alkyl group and a carbonyl group.

Specific examples of the compound represented by general formula (6) areas follows.

Specific examples of the compound represented by general formula (7) areas follows.

The content of the thermal acid generator (H) is preferably 0.1 part byweight or more, more preferably 0.3 part by weight or more, still morepreferably 0.5 part by weight or more, relative to 100 parts by weightof (A1) the polyimide, the polybenzoxazole, the polyimide precursor orthe polybenzoxazole precursor or (A2) the resin having such a backbonestructure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, from the viewpointof further accelerating the crosslinking reaction. On the other hand,the content is preferably 20 parts by weight or less, more preferably 15parts by weight or less, still more preferably 10 parts by weight orless, from the viewpoint of the electrical insulation properties of theheat-resistant resin film.

The resin composition according to the present invention may alsocontain an adhesion-improving agent. Examples of the adhesion-improvingagent include silane coupling agents such as vinyl trimethoxysilane,vinyl triethoxysilane, epoxy cyclohexyl ethyl trimethoxysilane,3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane,p-styryl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyl trimethoxysilane, titaniumchelate agents, aluminum chelate agents, and compounds obtained byreacting a aromatic amine compound with an alkoxy group-containingsilicon compound. Two or more of these adhesion-improving agents may becontained. When the adhesion-improving agent is contained, it becomespossible to enhance the close adhesion to an underlying base material,e.g., a silicon wafer, ITO, SiO₂ and nitride silicon, during thedevelopment of a photosensitive resin film. It becomes also possible toenhance the resistance to oxygen plasma, which is used for washingpurposes or the like, or an UV ozone treatment. The content of theadhesion-improving agent is preferably 0.1 to 10 parts by weightrelative to 100 parts by weight of (a1) the polyimide, thepolybenzoxazole, the polyimide precursor or the polybenzoxazoleprecursor or (A2) the resin having such a backbone structure that twocyclic structures are bonded to a cyclic-structure-constitutingquaternary carbon atom.

The resin composition according to the present invention may alsocontain a bonding-improving agent. Specific examples of thebonding-improving agent include an alkoxysilane-containing aromaticamine compound, an aromatic amide compound, and a silane compoundcontaining no aromatic moiety. Two or more of these bonding-improvingagents may be contained. When the compound is contained, it becomespossible to improve the bonding to a base material after burning orcuring. Specific examples of the alkoxysilane-containing aromatic aminecompound and the aromatic amide compound are shown below. In addition tothese compounds, a compound produced by reacting an aromatic aminecompound with an alkoxy-group-containing silicon compound may also beused. A specific example of the compound is a compound produced byreacting an aromatic amine compound with an alkoxysilane compound havinga group capable of reacting with an amino group such as an epoxy groupor a chloromethyl group.

Examples of the silane compound containing no aromatic moiety includevinyl silane compounds such as vinyl trimethoxysilane, vinyltriethoxysilane, vinyl trichlorosilane, and vinyltris(β-methoxyethoxy)silane, and carbon-carbon unsaturatedbond-containing silane compounds such as 3-methacryloxy propyltrimethoxysilane, 3-acryloxy propyl trimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxy propyl methyl dimethoxysilane, and3-methacryloxy propyl methyl diethoxysilane. Among these compounds,vinyltrimethoxysilane and vinyltriethoxysilane are preferred.

The content of the bonding-improving agent is preferably 0.01 to 15parts by weight relative to 100 parts by weight of (A1) the polyimide,the polybenzoxazole, the polyimide precursor or the polybenzoxazoleprecursor or (A2) the resin having such a backbone structure that twocyclic structures are bonded to a cyclic-structure-constitutingquaternary carbon atom.

A compound which can act as both of an adhesion-improving agent and abonding-improving agent, such as vinyltrimethoxysilane andvinyltriethoxysilane, may also be contained.

The resin composition according to the present invention may contain asurfactant to improve the wettability with a substrate.

Specific examples of the surfactant include: a fluorine-containingsurfactant, such as Florad (a product name, manufactured by Sumitomo 3MInc.), Megaface (a product name, manufactured by DIC Corporation) andSurflon (a product name, manufactured by Asahi Glass Co., Ltd.); anorganic siloxane surfactant, such as KP341 (a product name, manufacturedby Shin-Etsu Chemical Co., Ltd.), DBE (a product name, manufactured byChisso Corporation), Glanol (a product name, manufactured by KyoeishaChemical Co., Ltd.) and BYK (manufactured by BYK-Chemie); and an acrylicpolymer surfactant, such as Polyflow (a product name, manufactured byKyoeisha Chemical Co., Ltd.).

Next, the method for producing the resin composition according to thepresent invention will be described. The resin composition can beproduced by, for example, dissolving the components (A), (B) and (D),the component (C), and optionally the components (E) to (H), theadhesion-improving agent, the bonding-improving agent, the surfactantand the like. Examples of the method for the dissolution includestirring and heating. When heating is employed, it is preferred toadjust the heating temperature to a temperature falling within a rangeat which the performance of the resin composition cannot bedeteriorated, and the heating temperature is generally room temperatureto 80° C. The order of dissolution of the components is not particularlylimited. For example, a method can be mentioned, in which the compoundsare dissolved in order of increasing solubility. With respect to acomponent that is likely to generate bubbles during stirring ordissolution, such as surfactants and some types of adhesion-improvingagents, the component can be added finally after all of the othercomponents are dissolved, thereby preventing the insufficientdissolution of the other components due to the generation of thebubbles.

It is preferred that the resin composition thus produced is filteredthrough a filtration filter to remove foreign matters and particles. Thefilter pore size is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm or0.02 μm, but is not limited thereto. Specific examples of the materialfor the filtration filter include polypropylene (PP), polyethylene (PE),nylon (NY) and polytetrafluoroethylene (PTFE), and polyethylene andnylon are preferred. In the case where an organic pigment is containedin the resin composition, it is preferred to use a filtration filterhaving a larger pore size than the particle diameters of the organicpigment.

Next, the method for producing the heat-resistant resin film using theresin composition according to the present invention will be described.The resin composition according to the present invention is applied by aspin coating method, a slit coating method, a dip coating method, aspray coating method, a printing method or the like to produce a coatingfilm of the resin composition. From the viewpoint of the applicationonto a large-size substrate, the improvement in productivity and thelike, the application of the resin composition is preferably carried outby slit coating. Prior to the application, a base material onto whichthe resin composition is to be applied may be pre-treated with theabove-mentioned adhesion-improving agent. For example, a method can bementioned, in which the surface of the base material is treated by, forexample, spin coating, slit die coating, bar coating, dip coating, spraycoating or a treatment with steam using a solution prepared bydissolving the adhesion-improving agent in a solvent, such asisopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycolmonomethyl ether acetate, propylene glycol monomethyl ether, ethyllactate and diethyl adipate, at a concentration of 0.5 to 20% by weight.If necessary, it is possible to carry out a drying treatment underreduced pressure and then carry out a heat treatment at 50 to 300° C. toallow the reaction of the base material with the adhesion-improvingagent to proceed the reaction between the base material and theadhesion-improving agent.

Subsequently, the coating film of the resin composition is dried toproduce a photosensitive resin film. It is preferred to carry out thedrying at 50 to 150° C. for 1 minute to several hours with an oven, ahot plate, infrared ray or the like.

Subsequently, an actinic ray is emitted over the photosensitive resinfilm through a mask having a desired pattern. Examples of the actinicray to be used for the exposure include ultraviolet ray, visible ray,electron beam and X-ray. In the present invention, it is preferred touse i line (365 nm), h line (405 nm) or g line (436 nm) of a mercurylamp.

Subsequently, the photosensitive resin film exposed to light isdeveloped to remove the exposed range. The developer is preferably anaqueous solution of an alkaline compound such as tetramethyl ammonium,diethanolamine, diethylaminoethanol, sodium hydroxide, potassiumhydroxide, sodium carbonate, potassium carbonate, triethylamine,diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate,dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine,ethylenediamine, or hexamethylenediamine.

In some cases, one or more of polar solvents such asN-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide,dimethylsulfoxide, γ-butyrolactone, and dimethylacrylamide, alcoholssuch as methanol, ethanol, and isopropanol, esters such as ethyl lactateand propylene glycol monomethyl ether acetate, and ketones such ascyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutylketone may be added to these aqueous alkali solutions. After thedevelopment, a rinsing treatment with water is generally carried out.The rinsing treatment may be carried out using a solution prepared byadding an alcohol, e.g., ethanol and isopropyl alcohol, or an ester,e.g., ethyl lactate and propylene glycol monomethyl ether acetate, towater.

The photosensitive resin film thus produced is subjected to a heattreatment to produce a heat-resistant resin film. The term “heattreatment” as used herein refers to a treatment of heating at atemperature falling within the range from 200 to 350° C. For example, amethod in which the heat treatment is carried out at 250° C. for 60minutes can be mentioned.

The heat-resistant resin film produced from the resin compositionaccording to the present invention can be used suitably as an insulatingfilm or a protective film for wiring lines. For example, theheat-resistant resin film can be used as an insulating film or aprotective film for wiring lines made from copper, aluminum or the likein a printed substrate produced by forming the wiring lines on a film orsubstrate made from polyimide, ceramic or the like, or as a protectivefilm for use in partial soldering of the wiring lines. In the case wherethe resin composition contains an electrically conductive filler, theheat-resistant resin film can also be used as a wiring material.

The heat-resistant resin film produced from the resin compositionaccording to the present invention can also be used suitably as aplanarization film in a display device equipped with a substrate havingTFTs formed thereon, the planarization film and display elements in thisorder. Examples of the display device having this configuration includea liquid crystal display device and an organic EL display device. Anactive-matrix-type display device has such a configuration that: TFTsand wiring lines which are respectively positioned on the side of theTFTs and which are connected to the TFTs are arranged on a glass- orplastic-made substrate; a planarization film is arranged on the wiringlines and the TFTs in such a manner as to cover projections anddepressions on the wiring lines and the TFTs; and display elements arearranged on the planarization film. The display elements and the wiringlines are connected to each other through contact holes formed in theplanarization film. In FIG. 1, the cross-sectional view of a TFTsubstrate is illustrated. Bottom-gate-type or top-gate-type TFTs 1 areprovided in a matrix shape on a substrate 6, an insulating film 3 isformed in such a manner as to cover the TFTs 1. Wiring lines 2, whichare respectively connected to the TFTs 1, are provided on the insulatingfilm 3. A planarization film 4 is also provided on the insulating film 3in such a manner that the wiring lines 2 are embedded in theplanarization film 4. Contact holes 7, which reach the wiring lines 2,are formed in the planarization film 4. ITOs (transparent electrodes) 5are formed on the planarization film 4 in such a manner that the ITOs 5are connected to the wiring lines 2 respectively through the contactholes 7. The ITOs 5 serve as electrodes for display elements (e.g.,organic EL elements). The organic EL elements may be of atop-emission-type which can emit luminescent light from a side opposedto the substrate 6 or a bottom-emission-type from which light can beextracted from the substrate 6 side, and is preferably of atop-emission-type. In this manner, an active-matrix-type organic ELdisplay device, in which TFTs 1 for driving organic EL elements areconnected to the organic EL elements, is produced.

In the case of an organic EL display device using TFTs in each of whicha semiconductor layer is made from amorphous silicon, microcrystalsilicon, a metal oxide (e.g., IGZO) or the like, there may be caseswhere an undesirable phenomenon, such as the deterioration ormalfunctions of the device, the development of a leakage current in thedevice or the like, is caused as the result of the penetration of lighthaving a relatively high energy, e.g., ultraviolet light or visiblelight in a short wavelength range. The heat-resistant resin filmproduced from the resin composition according to the present inventionhas an absorption at a wavelength of 300 to 460 nm. Therefore, in theorganic EL display device equipped with the heat-resistant resin film,the deterioration or malfunctions of the device, the development of aleakage current in the device or the like can be prevented and stabledriving/luminous properties can be achieved in the device.

An organic EL display device using TFTs in each of which a semiconductorlayer is made from a metal oxide is particularly preferably ahigh-resolution device. The degree of resolution is preferably 100 ppior more, more preferably 200 ppi or more. When the heat-resistant resinfilm produced from the resin composition according to the presentinvention is used in the high-resolution organic EL device, it becomespossible to more efficiently prevent the occurrence of an undesirablephenomenon, such as the deterioration or malfunctions of the device orthe development of a leakage current in the device which can be causedby the penetration of light.

In addition, the heat-resistant resin film produced from the resincomposition according to the present invention can be used suitably as:a surface protective film or an interlayer insulating film forsemiconductor devices including LSIs; a bonding agent or an underfillingagent to be used in the packaging of devices; a capping agent forpreventing the migration of copper; a planarization film for on-chipmicrolenses for solid-state imaging elements and various types ofdisplays and solid-state imaging elements; and others.

Next, the second aspect of the present invention will be described indetail.

The present invention provides a resin composition which is configuredsuch that, when the resin composition is formed into a resin compositionfilm that has a thickness of 3.0 μm after a heat treatment at atemperature within the range from 200 to 350° C., the resin compositionfilm forms a heat-resistant resin film having a light transmittance of50% or more at a wavelength of 365 to 436 nm before a heat treatment andhaving a light transmittance of 10% or less at a wavelength of 365 to436 nm after the heat treatment. The term “resin composition whichenables the formation of a heat-resistant resin film that has a lighttransmittance of 10% or less at a wavelength of 365 to 436 nm after theheat treatment” refers to a resin composition which enables theformation of a heat-resistant resin film that has a light transmittanceof 10% or less at a wavelength of 365 to 436 nm when the heat-resistantresin film is subjected to a heat treatment at a temperature of 200 to350° C. An organic EL display or the like equipped with theheat-resistant resin film does not undergo deterioration ormalfunctions, the development of a leakage current therein or the likewhich can be caused by the penetration of light into TFTs for drivingthe device. Therefore, the resin composition has an effect of improvingthe reliability of an organic EL display. When the heat-resistant resinfilm does not have a thickness of 3.0 μm after a heat treatment, thelight transmittance of the heat-resistant resin film can be determinedby converting the thickness of the heat-resistant resin film to 3.0 μmin accordance with the Lambert's law.

The resin composition according to the present invention contains acompound which does not have an absorption maximum at a wavelength of340 nm or more and less than 436 nm and has an absorption maximum at awavelength of 436 to 750 nm inclusive. This is preferred, because theresin composition can absorb visible light in the whole wavelength rangeand therefore a contrast-improving effect can also be imparted to theresin composition.

It is also preferred that the resin composition according to the presentinvention contains a photo-acid generator and therefore haspositive-working photosensitivity.

The resin composition according to present invention is a resincomposition which contains (A) an alkali-soluble resin, (I) a compoundwhose maximum absorption wavelength shifts by a heat treatment, (C) aphoto-acid generator, and (D) a solvent, and has positive-workingphotosensitivity.

The resin composition according to the present invention contains (A) analkali-soluble resin. The term “alkali-soluble” as used herein refers toa state that, when a solution prepared by dissolving the resin inγ-butyrolactone is applied onto a silicon wafer and is then pre-baked at120° C. for 4 minutes to form a prebaked film having a film thickness of10 μm±0.5 μm, then the prebaked film is immersed in a 2.38-wt % aqueoustetramethylammonium hydroxide solution at 23±1° C. for 1 minute, andthen the resultant film is rinsed with purified water, the dissolutionrate that is determined from the amount of decrease in the filmthickness is 50 nm/min. or more.

Examples of the alkali-soluble resin (A) include, but not limited to, apolyimide, a polyimide precursor, a polybenzoxazole, a polybenzoxazoleprecursor, a polyaminoamide, a polyamide, a polymer produced from aradically polymerizable monomer having an alkali-soluble group, a resinhaving such a backbone structure that two cyclic structures are bondedto a cyclic-structure-constituting quaternary carbon atom, a phenolicresin and/or a polyhydroxystyrene resin, a cyclic olefin polymer, and apolysiloxane. Two or more of these resins may be contained. Among thesealkali-soluble resins, those resins which have excellent heat resistanceand generate an outgas in a reduced volume under high-temperatureconditions are preferred. Specifically, at least one alkali-solubleresin selected from a polyimide, a polyimide precursor and apolybenzoxazole precursor or a copolymer of the at least onealkali-soluble resin is preferred.

The resin composition according to the present invention contains (A1) apolyimide, a polybenzoxazole, a polyimide precursor or a polybenzoxazoleprecursor.

These resins produce a small degassing amount under a high temperatureof 200° C. or higher after a heat treatment, have excellent heatresistance, and can exhibit excellent properties for use as aplanarization film or an insulating layer used in organic light emittingdevices and display elements or for the formation of a partition wall inthe devices.

With respect to the component (A1) to be used in the present invention,the polyimide is not particularly limited as long as it has an imidering, and the polybenzoxazole is not particularly limited as long as ithas a benzoxazole ring. The polyimide precursor is not particularlylimited as long as it has a structure that can be dehydrated andring-closed to produce a polyimide having an imide ring. Thepolybenzoxazole precursor is not particularly limited as long as it hasa structure that can be dehydrated and ring-closed to produce apolybenzoxazole having a benzoxazole ring. In the present invention, thecomponent (A1) is more preferably a polyimide precursor or apolybenzoxazole precursor, and more preferably contains a structuralunit represented by general formula (1) as the main component.

In general formula (1), R¹ and R² may be the same as or different fromeach other, and independently represent a bivalent to octavalent organicgroup having 2 or more carbon atoms. The bivalent to octavalent organicgroup having 2 or more carbon atoms may be a group in which —CH₂— issubstituted by —CO—, —COO—, —NH—, —NHCO—, —O—, —S—, —SO₂—, —Si— or—Si(CH₃)₂—, or may be a group in which a hydrogen atom contained thereinis substituted by a fluoroalkyl group, a hydroxyl group, an alkoxylgroup, a nitro group, a cyano group, a fluorine atom, a chlorine atom or—COOR¹′. R¹′ represents a hydrogen atom or an alkyl group having 1 to 20carbon atoms. R³ and R⁴ may be the same as or different from each other,and independently represent a hydrogen atom or an alkyl group having 1to 20 carbon atoms. a and b independently represent an integer of 0 to4, and c and d independently represent an integer of 0 to 2. Providedthat a+b>0.

The above-shown general formula (1) represents a polyimide precursor ora polybenzoxazole precursor each having a hydroxyl group, which hassuperior solubility in an aqueous alkaline solution due to the presenceof the hydroxyl group, compared with a polyimide precursor or apolybenzoxazole precursor each having no hydroxyl group.

Each of the polyimide precursor and the polybenzoxazole precursor is aresin having an amide bond in the main chain thereof, and is generallycomposed of an amine component and an acid component. Each of thepolyimide precursor and the polybenzoxazole precursor can be dehydratedand ring-closed by a heat treatment or a chemical treatment to producethe above-mentioned polyimide or polybenzoxazole. The number of repeatsof the structural unit in the present invention is preferably 10 to100000. Specific examples of the polyimide precursor include a polyamicacid ester and a polyisoimide, and a polyamic acid ester is preferred.Specific examples of the polybenzoxazole precursor include apolyhydroxyamide, a polyaminoamide, a polyamide and a polyamideimide,and a polyhydroxyamide is preferred. In each of the polyimide precursorand the polybenzoxazole precursor, it is preferred that an acid residueor an amine residue has an acidic group or an acidic group derivativesuch as OR⁵, SO₃R⁵, CONR⁵R⁶, COOR⁵ and SO₂NR⁵R⁶, more preferably ahydroxyl group, from the viewpoint of the solubility in an aqueousalkaline solution. R⁵ and R⁶ independently represent a hydrogen atom, ahydrocarbon group having 1 to 20 carbon atoms or a group having such astructure that a hydrogen atom in a hydrocarbon group having 1 to 20carbon atoms is substituted by another type of atom. The term “acidicgroup” refers to a case where all of R⁵'s or R⁶'s are hydrogen atoms,and the term “acidic group derivative” refers to a case where ahydrocarbon group having 1 to 20 carbon atoms or a group having such astructure that a hydrogen atom in a hydrocarbon group having 1 to 20carbon atoms is substituted by another type of atom is contained in R⁵or R⁶.

In the present invention, preferred examples of the structure of an acidcomponent to be used in the production of the polyimide precursor andthe polybenzoxazole precursor are shown below. Structures in each ofwhich 1 to 4 hydrogen atoms is substituted by an alkyl group having 1 to20 carbon atoms, a fluoroalkyl group, an alkoxyl group, an ester group,a nitro group, a cyano group, a fluorine atom or a chlorine atom canalso be included in the preferred examples.

In the formulas, J represents a direct bond, —COO—, —CONH—, —CH₂—,—C₂H₄—, —O—, —C₃H₆—, —SO₂—, —S—, —Si(CH₃)₂—, —O—Si(CH₃)₂—O—, —C₆H₄—,—C₆H₄—O—C₆H₄—, —C₆H₄—C₃H₆—C₆H₄—, or —C₆H₄—C₃F₆—C₆H₄—.

Examples of the acid component to be used in the production of thepolyimide precursor and the polybenzoxazole precursor include adicarboxylic acid, a tricarboxylic acid and a tetracarboxylic acid.

Preferred examples of the dicarboxylic acid include terephthalic acid,isophthalic acid, diphenyl ether dicarboxylic acid,bis(carboxyphenyl)hexafluoropropane, biphenyldicarboxylic acid,benzophenone dicarboxylic acid and triphenyldicarboxylic acid.

Specific examples of the tricarboxylic acid include trimellitic acid,trimesic acid, diphenyl ether tricarboxylic acid andbiphenyltricarboxylic acid.

Examples of the tetracarboxylic acid may include aromatictetracarboxylic acids such as pyromellitic acid,3,3′,4,4′-biphenyltetracarboxylic acid,2,3,3′,4′-biphenyltetracarboxylic acid,2,2′,3,3′-biphenyltetracarboxylic acid,3,3′,4,4′-benzophenonetetracarboxylic acid,2,2′,3,3′-benzophenonetetracarboxylic acid,2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane,2,2-bis(2,3-dicarboxyphenyl)hexafluoropropane,1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane,bis(3,4-dicarboxyphenyl)methane, bis(2,3-dicarboxyphenyl)methane,bis(3,4-dicarboxyphenyl)sulfone, bis(3,4-dicarboxyphenyl)ether,1,2,5,6-naphthalenetetracarboxylic acid,2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylicacid, and 3,4,9,10-perylenetetracarboxylic acid, and aliphatictetracarboxylic acids such as butanetetracarboxylic acid and1,2,3,4-cyclopentanetetracarboxylic acid.

It is more preferred to use an acid produced by substituting each of theabove-exemplified dicarboxylic acids, tricarboxylic acids andtetracarboxylic acids by 1 to 4 acidic groups or acidic groupderivatives (e.g., OR⁵ groups, SO₃R⁵ groups, CONR⁵R⁶ groups, COOR⁵groups and SO₂NR⁵R⁶ groups), preferably 1 to 4 hydroxyl groups orsulfonic acid groups, sulfonic acid amide groups, sulfonic acid estergroups or the like. R⁵ and R⁶ independently represent a hydrogen atom ora monovalent hydrocarbon group having 1 to 20 carbon atoms.

Each of these acids may be used without any modification or withmodification into an acid anhydride or an active ester. These acids maybe used singly, or two or more of them may be used in combination.

A silicon-atom-containing tetracarboxylic acid, such asdimethylsilanediphthalic acid and 1,3-bis(phthalicacid)tetramethyldisiloxane, can also be used to improve the bonding to asubstrate and the resistance to oxygen plasma to be used in washing orthe like or a UV ozone treatment. It is preferred that thesilicon-atom-containing tetracarboxylic acid is used in an amount of 0to 30 mol % relative to the total amount of the acid components.

In the present invention, examples of the preferred structure of theamine component to be used in the production of the polyimide precursoror the polybenzoxazole precursor are shown below. In addition, variantsof the structures, in each of which 1 to 4 hydrogen atoms areindependently substituted by an alkyl group having 1 to 20 carbon atoms,a fluoroalkyl group, an alkoxyl group, an ester group, a nitro group, acyano group, a fluorine atom or a chlorine atom are also preferred.

In the formulas, J represents a direct bond, —CO—, —COO—, —CONH—, —CH₂—,—C₂H₄—, —O—, —C₃H₆—, —C₃F₆—, —C₁₃H₈—, —SO₂—, —S—, —Si(CH₃)₂—,—O—Si(CH₃)₂—O—, —C₆H₄—, —C₆H₄—O—C₆H₄—, —C₆H₄—C₃H₆—C₆H₄—, or—C₆H₄—C₃F₆—C₆H₄—. R⁷ to R⁹ independently represent a hydrogen atom or amonovalent hydrocarbon group having 1 to 20 carbon atoms, and arepreferably monovalent alkyl groups each having 1 to 20 carbon atoms.

As the amine component to be used in the production of the polyimideprecursor and the polybenzoxazole precursor, a diamine can be used.

Preferred examples of the diamine may include hydroxyl group-containingdiamines such as bis(3-amino-4-hydroxyphenyl)hexafluoropropane,bis(3-amino-4-hydroxyphenyl)sulfone,bis(3-amino-4-hydroxyphenyl)propane,bis(3-amino-4-hydroxyphenyl)methylene,bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl,bis(3-amino-4-hydroxyphenyl)fluorene, carboxyl group-containing diaminessuch as 3,5-diaminobenzoic acid and 3-carboxy-4,4′-diaminodiphenylether, sulfonic acid-containing diamines such as 3-sulfonicacid-4,4-diaminodiphenyl ether, dithiohydroxyphenylenediamine,3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether,3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,3,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone,3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide,1,4-bis(4-aminophenoxy)benzene, benzidine, m-phenylenediamine,p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine,bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone,bis(4-aminophenoxy)biphenyl, bis{4-(4-aminophenoxy)phenyl}ether,1,4-bis(4-aminophenoxy)benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl,2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl,3,3′-diethyl-4,4′-diaminobiphenyl,2,2′,3,3′-tetramethyl-4,4′-diaminobiphenyl,3,3′,4,4′-tetramethyl-4,4′-diaminobiphenyl,2,2′-di(trifluoromethyl)-4,4′-diaminobiphenyl, or compounds eachresulting from replacing some hydrogen atoms of the aromatic ring ofeach of the foregoing by an alkyl group or a halogen atom, and aliphaticdiamines such as cyclohexyldiamine and methylenebiscyclohexylamine. Eachof these diamines may be substituted by an alkyl group having 1 to 10carbon atoms (e.g., a methyl group, an ethyl group), a fluoroalkyl grouphaving 1 to 10 carbon atoms (e.g., a trifluoromethyl group), or a groupsuch as F, Cl, Br and I. Each of the above-exemplified diaminespreferably has an acidic group or an acidic group derivative (e.g., OR⁵,SO₃R⁵, CONR⁵R⁶, COOR⁵, SO₂NR⁵R⁶), and more preferably has a hydroxylgroup. R⁵ and R⁶ independently represent a hydrogen atom or a monovalenthydrocarbon group having 1 to 20 carbon atoms.

These diamines may be used without any modification, or diisocyanatecompounds and trimethylsilylated diamines corresponding to the diaminesmay be used, and two or more of them may be used in combination. Inapplications in which heat resistance is required, it is preferred touse an aromatic diamine in an amount of 50 mol % or more relative to thetotal amount of the diamine components.

As the diamine component, a silicon-atom-containing diamine, such as1,3-bis(3-aminopropyl)tetramethyldisiloxane and1,3-bis(4-anilino)tetramethyldisiloxane, can also be used to improve thebonding to a substrate and the resistance to oxygen plasma to be used inwashing or the like or a UV ozone treatment. It is preferred that thesilicon-atom-containing diamine is used in an amount of 1 to 30 mol %relative to the total amount of the diamine components.

In the present invention, it is preferred to cap a terminal of thepolyimide precursor or the polybenzoxazole precursor by a monoamine, anacid anhydride, an acid chloride or a monocarboxylic acid each having ahydroxyl group, a carboxyl group, a sulfonic acid group or a thiolgroup. Two or more of these capping substances may be used incombination. When the resin has the above-mentioned group at a terminalthereof, it becomes possible to easily adjust the dissolution rate ofthe resin in an aqueous alkaline solution to a value within a desirablerange.

Examples of the monoamine include aniline, naphthylamine, andaminopyridine, compounds having a phenolic hydroxyl group, such as3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol,4-aminophenol, 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline,1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene,1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene,1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene,1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene,2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene,2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene,2-hydroxy-3-aminonaphthalene, and 1-amino-2-hydroxynaphthalene,compounds having a carboxyl group, such as 1-carboxy-8-aminonaphthalene,1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene,1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene,1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene,1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene,2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene,2-carboxy-4-aminonaphthalene, 2-carboxy-3-aminonaphthalene,1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinicacid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylicacid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-O-toluicacid, ammelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoicacid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, and4-aminobenzenesulfonic acid, and compounds having a thiol group, such as5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline,1-mercapto-8-aminonaphthalene, 1-mercapto-7-amino-naphthalene,1-mercapto-6-amino-naphthalene, 1-mercapto-5-aminonaphthalene,1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene,1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene,2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene,2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene,2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene,3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol,and 4-aminothiophenol.

Among them, preferred examples of the monoamine may include5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene,1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene,1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene,2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene,1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene,1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene,2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene,2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid,4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid,2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid,4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine,2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol,3-aminothiophenol, and 4-aminothiophenol. These monoamines may be usedsingly, or two or more of them may be used in combination.

Examples of the acid anhydride, the acid chloride, and themonocarboxylic acid include acid anhydrides such as phthalic anhydride,maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride,and 3-hydroxyphthalic anhydride, monocarboxylic acids such as2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol,3-carboxythiophenol, 4-carboxythiophenol,1-hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene,1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene,1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene,1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene,1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene,1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene,1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene,2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, and4-carboxybenzenesulfonic acid, and monoacid chloride compounds with thecarboxyl group of the monocarboxylic acid formed into an acid chloride,monoacid chloride compounds with only one carboxy group of dicarboxylicacids such as terephthalic acid, phthalic acid, maleic acid,cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid,5-norbornene-2,3-dicarboxylic acid, 1, 2-dicarboxynaphthalene,1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene,1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene,1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene,2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, and2,7-dicarboxynaphthalene formed into an acid chloride, and active estercompounds obtained by reaction of a monoacid chloride compound withN-hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3-dicarboxyimide.

Among them, preferred examples of the acid anhydride, the acid chloride,and the monocarboxylic acid may include acid anhydrides such as phthalicanhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylicanhydride, and 3-hydroxyphthalic anhydride, monocarboxylic acids such as3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol,4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene,1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene,1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene,1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, and4-carboxybenzenesulfonic acid, monoacid chloride compounds with thecarboxyl group of the monocarboxylic acid formed into an acid chloride,monoacid chloride compounds with only one carboxy group of dicarboxylicacids such as terephthalic acid, phthalic acid, maleic acid,cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene,1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, and2,6-dicarboxynaphthalene formed into an acid chloride, and active estercompounds obtained by reaction of a monoacid chloride compound withN-hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3-dicarboxyimide.These monoamines may be used singly, or two or more of them may be usedin combination.

The content of the terminal-capping agent (e.g., a monoamine, an acidanhydride, an acid chloride, a monocarboxylic acid) is preferably 0.1 to70 mol %, more preferably 5 to 50 mol %, relative to the number of molesof the acid component monomer or the diamine component monomer to becharged. When the content is adjusted to the above-mentioned value, itbecomes possible to produce a resin composition which has a propersolution viscosity during the application of the resin composition andcan exert excellent film properties.

The resin may also have a polymerizable functional group at a terminalthereof. Examples of the polymerizable functional group include anethylenically unsaturated bond group, an acethylene group, a methylolgroup and an alkoxymethyl group.

The terminal-capping agent introduced into the resin can be detectedeasily by the following methods. For example, the resin having theterminal-capping agent introduced thereinto is dissolved in an acidicsolution to decompose the resin into an amine component and an acidcomponent which are constituent units of the resin, and these componentsare subjected to a measurement by gas chromatography (GC) or NMR todetect the terminal-capping agent easily. Alternatively, the resinhaving the terminal-capping agent introduced thereinto may be directlysubjected to a measurement by thermal decomposition gas chromatography(PGC) or infrared or ¹³C-NMR spectroscopy to detect the terminal-cappingagent.

The reaction solvent which can be used preferably in the synthesis ofthe polyimide, the polybenzoxazole, the polyimide precursor or thepolybenzoxazole precursor in the present invention is not particularlylimited, as long as the polymer can be synthesized. Specific examples ofthe reaction solvent include: a polar aprotic solvent, such asN-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide,N,N-dimethylacetamide and dimethyl sulfoxide; a glycol ether, such astetrahydrofuran, dioxane, propylene glycol monomethyl ether, propyleneglycol monoethyl ether, diethylene glycol dimethyl ether, diethyleneglycol diethyl ether and diethylene glycol ethyl methyl ether; a ketone,such as acetone, methyl ethyl ketone, diisobutyl ketone and diacetonealcohol; an ester, such as ethyl acetate, butyl acetate, isobutylacetate, propyl acetate, propylene glycol monomethyl ether acetate,glycol ether acetate and 3-methyl-3-methoxy butyl acetate; an alcohol,such as ethyl lactate, methyl lactate, diacetone alcohol and3-methyl-3-methoxybutanol; and an aromatic hydrocarbon, such as tolueneand xylene. Two or more of these solvents may be contained. The contentof the solvent is preferably 100 to 2000 parts by weight relative to thetotal amount, i.e., 100 parts by weight, of the compound having an aminogroup and the compound having an acid anhydride group.

The resin composition according to the present invention contains (A2) aresin having such a backbone structure that two cyclic structures arebonded to a cyclic-structure-constituting quaternary carbon atom. Theresin having such a backbone structure that two cyclic structures arebonded to a cyclic-structure-constituting quaternary carbon atom is aresin having such a backbone structure that two cyclic structures arebonded to a cyclic-structure-constituting quaternary carbon atom, i.e.,a cardo structure. A common cardo structure is a structure in which abenzene ring is bonded to a fluorene ring.

Specific examples of the backbone structure in which two cyclicstructures are bonded to a cyclic-structure-constituting quaternarycarbon atom include a fluorene backbone, a bisphenolfluorene backbone, abisaminophenylfluorene backbone, a fluorene backbone having an epoxygroup, and a fluorene backbone having an acryl group.

The resin having such a backbone structure that two cyclic structuresare bonded to a cyclic-structure-constituting quaternary carbon atom canbe produced by polymerizing a backbone having the cardo structurethrough a reaction between functional groups bonding to the backbones orthe like. The resin having such a backbone structure that two cyclicstructures are bonded to a cyclic-structure-constituting quaternarycarbon atom has a structure in which the main chain is linked to ahighly bulky side chain through one element (i.e., a cardo structure),and has a cyclic structure in the direction substantially perpendicularto the main chain.

Specific example of the monomer having a cardo structure include: acardo-structure-containing bisphenol, such as abis(glycidyloxyphenyl)fluorene-type epoxy resin, 9,9-bis(4-hydroxyphenyl)fluorene and9,9-bis(4-hydroxy-3-methylphenyl)fluorene; a9,9-bis(cyanoalkyl)fluorene, such as 9,9-bis(cyanomethyl)fluorene; and a9,9-bis(aminoalkyl)fluorene, such as 9,9-bis(3-aminopropyl)fluorene.

The resin having such a backbone structure that two cyclic structuresare bonded to a cyclic-structure-constituting quaternary carbon atom isa polymer produced by polymerizing a monomer having a cardo structure,and may also be a copolymer of the monomer with another copolymerizablemonomer.

As the method for polymerizing the monomer, any conventional method canbe employed. Examples of the method include a ring openingpolymerization method and an addition polymerization method.

The resin composition according to the present invention contains (A3) aphenolic resin and/or a polyhydroxystyrene resin.

Specific examples of the phenolic resin that can be used in the presentinvention include a novolac resin and a resol resin. The phenolic resincan be produced by polycondensing a single type of phenol compound or amixture of two or more types of phenol compounds with an aldehyde suchas formalin.

Examples of the phenols constituting the novolak resin and the resoleresin include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol,2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol,3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol,2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol,methylenebisphenol, methylenebis-p-cresol, resorcinol, catechol,2-methylresorcinol, 4-methylresorcinol, o-chlorophenol, m-chlorophenol,p-chlorophenol, 2,3-dichlorophenol, m-methoxyphenol, p-methoxyphenol,p-butoxyphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol,2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, α-naphthol, andβ-naphthol, and these phenols may be used singly, or a mixture of two ormore of them may be used.

Specific examples of the aldehyde include formalin, paraformaldehyde,acetaldehyde, benzaldehyde, hydroxybenzaldehyde and chloroacetaldehyde.These aldehydes may be used singly, or a mixture of two or more of themmay be used.

The phenolic resin to be used in the present invention may be one havinga structure in which each of 1 to 4 of hydrogen atoms added to anaromatic ring is substituted by an alkyl group having 1 to 20 carbonatoms, a fluoroalkyl group, an alkoxyl group, an alkoxymethyl group, amethylol group, an ester group, a nitro group, a cyano group, a fluorineatom or a chlorine atom. The preferred weight average molecular weightof the phenolic resin to be used in the present invention is 2,000 to50,000, preferably 3,000 to 30,000, as determined in terms ofpolystyrene by employing gel permeation chromatography (GPC). When themolecular weight is 2,000 or more, the form of a pattern, resolution,developability and heat resistance become excellent. When the molecularweight is 50,000 or less, sufficient sensitivity can be secured.

Specific examples of the polyhydroxystyrene resin that can be used inthe present invention include: a polymer or a copolymer which isproduced by polymerizing an aromatic vinyl compound having a phenolichydroxyl group, such as p-hydroxystyrene, m-hydroxystyrene,o-hydroxystyrene, p-isopropenylphenol, m-isopropenylphenol ando-isopropenylphenol, singly or polymerizing two or more of the aromaticvinyl compounds by a known method; and a polymer or copolymer which isproduced by an addition reaction for adding an alkoxy group to a part ofa polymer or copolymer, which is produced by polymerizing an aromaticvinyl compound, such as styrene, o-methylstyrene, m-methylstyrene andp-methylstyrene, singly or polymerizing two or more of the aromaticvinyl compounds by a conventional known method, by a conventional knownmethod.

The aromatic vinyl compound having a phenolic hydroxyl group that can beused preferably is p-hydroxystyrene and/or m-hydroxystyrene, and styreneis used preferably as the aromatic vinyl compound.

The polyhydroxystyrene resin to be used in the present invention mayhave a structure in which each of 1 to 4 of hydrogen atoms added to thearomatic ring is substituted by an alkyl group having 1 to 20 carbonatoms, a fluoroalkyl group, an alkoxyl group, an alkoxymethyl group, amethylol group, an ester group, a nitro group, a cyano group, a fluorineatom or a chlorine atom.

The preferred weight average molecular weight of the polyhydroxystyreneresin to be used in the present invention is preferably 3,000 to 60,000,more preferably 3,000 to 25,000, as determined in terms of polystyreneby employing gel permeation chromatography (GPC). When the molecularweight is 3,000 or more, the form of a pattern, resolution,developability and heat resistance become excellent. When the molecularweight is 60,000 or less, sufficient sensitivity can be secured.

The resin composition according to the present invention contains acyclic olefin polymer. Examples of the cyclic olefin polymer that can beused in the present invention include a homopolymer and a copolymer of acyclic olefin monomer having a cyclic structure (an alicyclic oraromatic structure) and a carbon-carbon double bond. The cyclic olefinpolymer may also have a monomer other than the cyclic olefin monomer.

Examples of the monomer constituting the cyclic olefin polymer include acyclic olefin monomer having a protic polar group, a cyclic olefinmonomer having an aprotic polar group, a cyclic olefin monomer having nopolar group, and a monomer other than a cyclic olefin. The monomer otherthan a cyclic olefin may have a protic polar group or another polargroup, or may have no polar group.

Specific examples of the cyclic olefin monomer having a protonic polargroup include carboxyl group-containing cyclic olefins such as5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5-carboxymethyl-5-hydroxycarbonylbicyclo[2.2.1]hept-2-ene,5-exo-6-end-dihydroxycarbonylbicyclo[2.2.1]hept-2-ene,8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-hydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,and8-exo-9-end-dihydroxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,and hydroxyl group-containing cyclic olefins such as5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene,5-methyl-5-(4-hydroxyphenyl)bicyclo[2.2.1]hept-2-ene,8-(4-hydroxyphenyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene, and8-methyl-8-(4-hydroxyphenyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene.These monomers may be used singly, or two or more of them may be used incombination.

Specific examples of the cyclic olefin monomer having a polar groupother than a protonic polar group include cyclic olefins having an estergroup such as 5-acetoxybicyclo[2.2.1]hept-2-ene,5-methoxycarbonylbicyclo[2.2.1]hept-2-ene,5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene,8-acetoxytetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-ethoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-n-propoxycarbonyltetracyclo[4.4.0.11^(2,5).1^(7,10)]dodeca-3-ene,8-isopropoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-n-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-ethoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-n-propoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-isopropoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-n-butoxycarbonyltetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,and8-methyl-8-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,cyclic olefins having an N-substituted imide group such asN-phenyl-(5-norbornene-2,3-dicarboximide), cyclic olefins having a cyanogroup such as 8-cyanotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methyl-8-cyanotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene, and5-cyanobicyclo[2.2.1]hept-2-ene, and cyclic olefins having a halogenatom such as 8-chlorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene and8-methyl-8-chlorotetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene. Thesemonomers may be used singly, or two or more of them may be used incombination.

Specific examples of the cyclic olefin monomer having no polar groupinclude bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene,5-butyl-bicyclo[2.2.1]hept-2-ene, 5-ethylidene-bicyclo[2.2.1]hept-2-ene,5-methylidene-bicyclo[2.2.1]hept-2-ene,5-vinyl-bicyclo[2.2.1]hept-2-ene, tricyclo[4.3.0.1^(2,5)]deca-3,7-diene,tetracyclo[8.4.0.1^(11,14).0^(3,7)]pentadeca-3,5,7,12,11-pentaene,tetracyclo[4.4.0.1^(2,5).1^(7,10)]deca-3-ene,8-methyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-ethyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-methylidene-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-ethylidene-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-vinyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,8-propenyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,pentacyclo[6.5.1.1^(3,6).0^(2,7).0^(9,13)]pentadeca-3,10-diene,cyclopentene, cyclopentadiene,1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene,8-phenyl-tetracyclo[4.4.0.1^(2,5).1^(7,10)]dodeca-3-ene,tetracyclo[9.2.1.0^(2,10).0^(3,8)]tetradeca-3,5,7,12-tetraene,pentacyclo[7.4.0.1^(3,6).1^(10,13).0^(2,7)]pentadeca-4,11-diene, andpentacyclo[9.2.1.14,7.0^(2,10).0^(3,8)]pentadeca-5,12-diene. Thesemonomers may be used singly, or two or more of them may be used incombination.

Specific examples of the monomer other than the cyclic olefins includeα-olefins having 2 to 20 carbon atoms such as ethylene, propylene,1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene,3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene,4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene,3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 1-octadecene, and 1-eicosene, and chain olefins such asnon-conjugated dienes including 1,4-hexadiene, 4-methyl-1,4-hexadiene,5-methyl-1,4-hexadiene, and 1,7-octadiene. These monomers may be usedsingly, or two or more of them may be used in combination.

As the method for polymerizing the cyclic olefin polymer using theabove-mentioned monomer, any conventional method can be employed.Examples of the method include a ring opening polymerization method andan addition polymerization method.

The polymerization catalyst to be used in the polymerization ispreferably a complex of a metal such as molybdenum, ruthenium or osmium.These polymerization catalysts may be used singly, or two or more ofthem may be used in combination.

The hydrogenation of the cyclic olefin polymer produced by thepolymerization of the monomer is generally carried out using ahydrogenation catalyst. As the hydrogenation catalyst, one which isconventionally used in the hydrogenation of an olefin compound can beused. Specific examples of the hydrogenation catalyst to be used includea Ziegler-type homogeneous catalyst, a noble metal complex catalyst anda supported noble metal-based catalyst.

Among these hydrogenation catalysts, noble metal complex catalysts ofrhodium, ruthenium and the like are preferred, and a ruthenium catalystwith which a nitrogenated heterocyclic carbene compound or phosphine,which is a compound having a high electron-donating property,coordinates is particularly preferred, from the viewpoint of avoidingthe occurrence of a side reaction causing the deformation of afunctional group or the like and enabling the selective hydrogenation ofa carbon-carbon unsaturated bond in the polymer.

The resin composition according to the present invention contains apolysiloxane. An example of the polysiloxane that can be used in thepresent invention is a polysiloxane produced by the hydrolyticcondensation of at least one organosilane.

Specific examples of the organosilane include tetra-functional silanessuch as tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, andtetraphenoxysilane, tri-functional silanes such asmethyltrimethoxysilane, methyltriethoxysilane,methyltriisopropoxysilane, methyltri-n-butoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane,ethyltri-n-butoxysilane, n-propyltrimethoxysilane,n-propyltriethoxysilane, n-butyltrimethoxysilane,n-butyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane,decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane,3-methacryloxypropyltrimethoxysilane,3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane,phenyltrimethoxysilane, phenyltriethoxysilane,p-hydroxyphenyltrimethoxysilane,1-(p-hydroxyphenyl)ethyltrimethoxysilane,2-(p-hydroxyphenyl)ethyltrimethoxysilane,4-hydroxy-5-(p-hydroxyphenylcarbonyloxy)pentyltrimethoxysilane,trifluoromethyltrimethoxysilane, trifluoromethyltriethoxysilane,3,3,3-trifluoropropyltrimethoxysilane, 3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropyltriethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltriethoxysilane,[(3-ethyl-3-oxetanyl)methoxy]propyltrimethoxysilane,[(3-ethyl-3-oxetanyl)methoxy]propyltriethoxysilane,3-mercaptopropyltrimethoxysilane, 3-(trimethoxysilyl)propyl succinate,1-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane,1-naphthyltri-n-propoxysilane, 2-naphthyltrimethoxysilane,1-anthracenyltrimethoxysilne, 9-anthracenyltrimethoxysilne,9-phenanthrenyltrimethoxysilane, 9-fluorenyltrimethoxysilane,2-fluorenyltrimethoxysilane, 1-pyrenyltrimethoxysilane,2-indenyltrimethoxysilane, and 5-acenaphthenyltrimethoxysilane,di-functional silanes such as dimethyldimethoxysilane,dimethyldiethoxysilane, dimethyldiacetoxysilane,di-n-butyldimethoxysilane, diphenyldimethoxysilane,(3-glycidoxypropyl)methyldimethoxysilane,(3-glycidoxypropyl)methyldiethoxysilane, di(1-naphthyl)dimethoxysilane,and di(1-naphthyl)diethoxysilane, and mono-functional silanes such astrimethylmethoxysilane, tri-n-butylethoxysilane,(3-glycidoxypropyl)dimethylmethoxysilane, and(3-glycidoxypropyl)dimethylethoxysilane. Two or more of theseorganosilanes may be used in combination.

Specific examples of the organosilane oligomer include: methyl silicate51 (n: 4 on average) manufactured by Fuso Chemical Co., Ltd., M silicate51 (n: 3 to 5 on average), silicate 40 (n: 4 to 6 on average) andsilicate 45 (n: 6 to 8 on average) manufactured by Tama Chemicals Co.,Ltd., and methyl silicate 51 (n: 4 on average), methyl silicate 53A (n:7 on average) and ethyl silicate 40 (n: 5 on average) manufactured byColcoat Co., Ltd. These products can be purchased from these companies.Two or more of them may be used in combination.

The content of an Si atom derived from the organosilane in thepolysiloxane can be determined by determining the structure of a rawmaterial organosilane by ¹H-NMR, ¹³C-NMR, ²⁹Si-NMR, IR, TOF-MS or thelike and then calculating an integration ratio of a peak coming from anSi—C bond to a peak coming from an Si—O bond in IR spectra of thestructure.

The weight average molecular weight (Mw) of the polysiloxane is notparticularly limited, and is preferably 1,000 or more as determined interms of polystyrene by GPC (gel permeation chromatography), from theviewpoint of improving the coating film formability. On the other hand,the weight average molecular weight (Mw) is preferably 100,000 or less,more preferably 50,000 or less, from the viewpoint of the solubility ina developing solution.

The polysiloxane to be used in the present invention can be synthesizedby hydrolyzing and partially condensing a monomer, such as theabove-mentioned organosilane, or an oligomer. The term “partialcondensation” as used herein refers to a procedure by which several ofSi—OH groups can remain in the polysiloxane, rather than condensing allof Si—OH groups in a hydrolysis product. The hydrolysis and the partialcondensation can be carried out employing the conventional methods. Forexample, a method can be mentioned, in which a solvent, water andoptionally a catalyst are added to an organosilane mixture and theresultant solution is stirring under heating at 50 to 150° C. for about0.5 to 100 hours. If necessary, a hydrolysis by-product (an alcohol suchas methanol) or a condensation by-product (water) may be distilled awayby distillation during the stirring.

The catalyst is not particularly limited, and an acid catalyst and abasic catalyst are preferably used. Specific examples of the acidcatalyst include hydrochloric acid, nitric acid, sulfuric acid,hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid,formic acid, a polyhydric carboxylic acid, an anhydride of any one ofthese acids, and an ion exchange resin. Specific examples of the basiccatalyst include triethylamine, tripropylamine, tributylamine,tripentylamine, trihexylamine, triheptylamine, trioctylamine,diethylamine, triethanolamine, diethanolamine, sodium hydroxide,potassium hydroxide, an alkoxysilane having an amino group, and an ionexchange resin.

From the viewpoint of the storage stability of the photosensitive resincomposition, it is preferred that the catalyst is not contained in apolysiloxane solution after the hydrolysis and the partial condensation,and the removal of the catalyst may be carried out as required. Themethod for the removal is not particularly limited, and is preferablywashing with water and/or a treatment with an ion exchange resin fromthe viewpoint of the easiness of operation and the removability of thecatalyst. Washing with water is a method in which the polysiloxanesolution is diluted with a proper hydrophobic solvent and is then washedwith water several times to produce an organic layer, and the organiclayer is concentrated with an evaporator or the like. A treatment withan ion exchange resin is a method in which the polysiloxane solution isbrought into contact with a proper ion exchange resin.

The resin composition according to the present invention contains (I) acompound whose maximum absorption wavelength shifts by a heat treatment.The component (I) to be used in the present invention is preferably acompound having a maximum absorption wavelength of 340 nm or more andless than 450 nm after a heat treatment.

It is considered that it is preferred for an insulating layer or aplanarization film in an organic EL display to absorb light having awavelength of 340 to 450 nm, including ultraviolet light and visiblelight in a short wavelength range, which is believed to be greatlyinvolved in the occurrence of deterioration or malfunctions of thedevice or the development of a leakage current in the device caused bythe penetration of light into TFTs for driving the device. For theformation of an insulating layer or a planarization film having theeffect, it is considered to use a resin composition containing acompound having the maximum absorption wavelength thereof at 340 to 450nm, for example. When merely a resin composition containing a compoundhaving the maximum absorption wavelength thereof at 340 to 450 nm isused, however, the absorption of the light by the resin compositionoverlaps the absorption of g line (436 nm), h line (405 nm) and i line(365 am) which correspond to the main exposing light wavelengths of ahigh-pressure mercury lamp. Therefore, it is difficult to penetrate thelight to the bottom of the resin film during the exposure of the resinfilm to light to sensitize the resin film. In contrast, when (I) thecompound whose maximum absorption wavelength shifts by a heat treatmentaccording to the present invention is used, it becomes possible topenetrate light having a wavelength of the exposing light in aphotosensitive resin film that is not subjected to a heat treatment yet,and it becomes possible to absorb light having a wavelength of 340 to450 nm, including ultraviolet light and visible light in a shortwavelength range, in a heat-resistant resin film that has been subjectedto the heat treatment after the exposure to the light. By using theheat-resistant resin film as an insulating layer or a planarization filmin a display device, it becomes possible to prevent the occurrence ofdeterioration or malfunctions of the device or the development of aleakage current in the device which is caused as the result of thepenetration of light into TFTs for driving the device. It is preferredthat the component (I) has one or more phenolic hydroxyl groups, whereinone, several or all of the phenolic hydroxyl groups are respectivelyprotected by protecting groups. It is also preferred that each of theprotecting groups is a heat-labile group that can be removed with heator an acid-labile group that can be removed with an acid. Anelectronic/steric effect of the protecting group causes a change in thelevels of the HOMO (highest occupied molecular orbital) or an occupiedmolecular orbital close to the HOMO and the LUMO (lowest unoccupiedmolecular orbital) or an unoccupied molecular orbital close to the LUMOof a compound, leading to the shift of the maximum absorption wavelengthinherent in the compound. As a result, ultraviolet light and visiblelight in a short wavelength range, which are light having a wavelengthof light emitted by a high-pressure mercury lamp, can reach the bottomof the photosensitive resin film, resulting in the achievement of highsensitivity. Furthermore, because the protecting group can bedeprotected in the heat treatment step or a step prior to the heattreatment step, the absorption of the compound is recovered to anoriginal position thereof and, therefore, a heat-resistant resin filmhaving a function of absorbing light having a wavelength of 340 to 450nm can be produced finally.

The protecting group that can be removed with heat or an acid ispreferably any one of groups represented by general formula (8) to (11).

In general formula (8), R⁵⁹ to R⁶¹ may be the same as one another or oneor some of R⁵⁹ to R⁶¹ may be different from the others, andindependently represent a hydrogen atom or a monovalent hydrocarbongroup having 1 or more carbon atoms; in general formula (9), nrepresents 0 or 1; in general formula (10), R⁶² represents a monovalenthydrocarbon group having 1 to 20 carbon atoms; and in general formula(11), Z represents an oxygen atom, a sulfur atom or —N(R⁶³)—, R⁶⁴represents a monovalent hydrocarbon group having 1 to 20 carbon atoms,and R⁶³ represents a hydrogen atom or a monovalent hydrocarbon grouphaving 1 to 20 carbon atoms.

Among these groups, an acetyl group, a tetrahydropyranyl group, atert-butoxycarbonyl group, an alkylamide group, an arylamide group, andthe like are preferred. These protecting groups can be introduced by aconventional known method (see, for example, “Courses in ExperimentalChemistry”, edited by Chemical Society of Japan (2005)). For example, inthe case where a phenolic hydroxyl group is protected by an acetylgroup, the protection can be achieved by reacting the compound having aphenolic hydroxyl group with acetic anhydride in pyridine.

In the component (I), the ratio of protection of a phenolic hydroxylgroup by the protecting group is preferably 50 mol % or more, morepreferably 70 mol % or more. The ratio of protection can be determinedby measuring NMR of the protected compound and then calculating theintegration ratio of a peak coming from a phenolic hydroxyl group to apeak coming from another structure. When 50 mol % or more of phenolichydroxyl groups contained in the component (I) are protected, the widthof shift of the maximum absorption wavelength which is caused by theprotecting group increases, and therefore light having the samewavelength as that of exposing light can penetrate more easily,resulting in the further increase in sensitivity.

It is preferred that (I) the compound whose maximum absorptionwavelength shifts by a heat treatment to be used in the presentinvention is a non-condensed polycyclic compound or a condensedpolycyclic compound each having at least one phenolic hydroxyl group. Itis also preferred that (I) the compound whose maximum absorptionwavelength shifts by a heat treatment to be used in the presentinvention is a non-condensed polycyclic compound or a condensedpolycyclic compound each having at least one phenolic hydroxyl group andalso having 2 to 8 inclusive of aromatic rings. Examples of thenon-condensed polycyclic compound or the condensed polycyclic compoundeach having at least one phenolic hydroxyl group include, but notlimited to, a benzophenone-type compound, a benzotriazole-type compound,a triazine-type compound, a benzoxazinone-type compound and ananthraquinone-type compound.

Examples of the benzophenone-type compounds include, but are not limitedto, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone,2-hydroxy-4-benzyloxybenzophenone,2-hydroxy-4-methoxy-5-sulfobenzophenone,2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate,2-hydroxy-4-methoxy-2′-carboxybenzophenone,2-hydroxy-4-octadesiloxybenzophenone,2-hydroxy-4-diethylamino-2′-hexyloxycarbonylbenzophenone,2,2′-dihydroxy-4-methoxybenzophenone,2,2′,4,4′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone,2,2′-dihydroxy-4,4′-dimethoxybenzophenone,1,4-bis(4-benzyloxy-3-hydroxyphenoxy)butane, and2,2′,3,4,4′-pentahydroxybenzophenone.

Examples of the benzotriazole-type compounds include, but are notlimited to, 2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5′-t-butylphenyl)benzotriazole,2-(2′-hydroxy-3′-t-butyl-5′-methylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-t-butylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′-t-butyl-5′-(2-(octyloxycarbonyl)ethyl)phenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′-dodecyl-5′-methylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-t-amylphenyl)benzotriazole,2-(2′-hydroxy-5′-t-octylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-(dimethylbenzyl)phenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2,2′-methylene-bis(2-(2′-hydroxy-5′-t-octylphenyl)benzotriazole), and2-(2′-hydroxy-3′-(3,4,5,6-tetrahydrophthalimidylmethyl)-5′-methylbenzylphenyl)benzotriazole.

Examples of the triazine-type compounds include, but are not limited to,2-(4-hexyloxy-2-hydroxyphenyl)-4,6-diphenyl-1,3,5-triazine,2-(4-octyloxy-2-hydroxyphenyl)-4,6-di(2,5-dimethylphenyl)-1,3,5-triazine,2-(4-butoxy-2-hydroxyphenyl)-4,6-di(4-butoxyphenyl)-1,3,5-triazine,2-(4-butoxy-2-hydroxyphenyl)-4,6-di(2,4-dibutoxyphenyl)-1,3,5-triazine,2-(4-(3-(2-ethylhexyloxy)-2-hydroxypropoxy)-2-hydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-1,3,5-triazine,2-(4-(3-dodecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl)-4,6-di(2,4-dimethylphenyl)-1,3,5-triazine,2,4-di(4-butoxy-2-hydroxyphenyl)-6-(4-butoxyphenyl)-1,3,5-triazine, and2,4-di(4-butoxy-2-hydroxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-triazine.

A specific example of the benzoxazinone-type compound includes, but isnot limited to,2,2′-p-phenylenebis(6-hydroxy-4H-3,1-benzoxazine(oxazin)-4-one).

Examples of the anthraquinone-type compounds include, but are notlimited to, 1-hydroxyanthraquinone, 2-hydroxyanthraquinone,3-hydroxyanthraquinone, 1-hydroxy-2-methoxyanthraquinone,1,2-dihydroxyanthraquinone, 1,3-dihydroxyanthraquinone,1,4-dihydroxyanthraquinone, 1,5-dihydroxyanthraquinone,1,8-dihydroxyanthraquinone, 1,3-dihydroxy-3-methylanthraquinone,1,5-dihydroxy-3-methylanthraquinone,1,6-dihydroxy-3-methylanthraquinone,1,7-dihydroxy-3-methylanthraquinone,1,8-dihydroxy-3-methylanthraquinone,1,8-dihydroxy-2-methylanthraquinone,1,3-dihydroxy-2-methoxyanthraquinone,2,4-dihydroxy-1-methoxyanthraquinone,2,5-dihydroxy-1-methoxyanthraquinone,2,8-dihydroxy-1-methoxyanthraquinone,1,8-dihydroxy-3-methoxy-6-methylanthraquinone,1,2,3-hydroxyanthraquinone, and 1,3,5-trihydroxyanthraquinone.

These compounds may be used singly, or two or more of them may be usedin combination.

The component (I) to be used in the present invention is preferablysoluble in an organic solvent. The term “soluble in an organic solvent”as used herein refers to a case where a substance is dissolved in atleast one solvent selected from N-methyl-2-pyrrolidone,gamma-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide,dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycolmonomethyl ether, acetone, methyl ethyl ketone, diisobutyl ketone,diacetone alcohol, 3-methyl-3-methoxybutanol, ethyl acetate, propyleneglycol monomethyl ether acetate, ethyl lactate, toluene and xylene at aconcentration of 10% by weight or more at 23° C. When the component (I)is soluble in an organic solvent, a bonding property can be furtherimproved during development and the breakdown voltage of the film aftera heat treatment can also be improved without causing the aggregation ofthe component (I) in the photosensitive resin composition.

In the present invention, the content of the component (I) is preferably5 to 300 parts by weight, particularly preferably 10 to 200 parts byweight, relative to 100 parts by weight of the alkali-soluble resin (A).When the amount of the component (I) used is 5 parts by weight or more,the light transmittance of the cured film to light having a wavelengthwithin an ultraviolet to visible light wavelength range can bedecreased. When the amount is 300 parts by weight or less, the waterabsorption ratio can be reduced while maintaining the strength of thecured film.

The term “heating treatment” as used herein refers to a procedure ofheating at a temperature falling within the range from 200 to 350° C.,more preferably 230° C. or higher. When the heat treatment is carriedout at 230° C. or higher, the protecting group is removed efficiently,thereby causing the shift of the maximum absorption wavelength of theheat-resistant resin film after the heat treatment. The heat treatmentmay be carried out under a nitrogen atmosphere or in air.

The resin composition according to the present invention contains (C) aphoto-acid generator. Specific examples of the photo-acid generator (C)include a quinone diazide compound, a sulfonium salt, a phosphoniumsalt, a diazonium salt and an iodonium salt.

Examples of the quinone diazide compound include: a compound produced bybonding quinone diazide sulfonic acid to a polyhydroxyl compound or apolyamino compound via an ester bond; a compound produced by bondingquinone diazide sulfonic acid to a polyhydroxyl compound via asulfoneamide bond; and a compound produced by bonding quinone diazidesulfonic acid to a polyhydroxyl polyamino compound via an ester bondand/or a sulfoneamide bond. In these compounds, it is preferred that 50mol % or more of all of functional groups in the polyhydroxyl compoundor the polyamino compound is substituted by quinone diazide. When aquinone diazide compound in which 50 mol % or more is substituted isused, the affinity of the quinone diazide compound for an aqueousalkaline solution is reduced, the solubility of an unexposed part of theresin composition in an aqueous alkaline solution is greatly reduced,and the quinone diazide sulfonyl group is converted to an indenecarboxylic acid upon exposure to light to achieve a high dissolutionrate of an exposed part of the resin composition in an aqueous alkalinesolution, resulting in the increase in the ratio of the dissolution rateof the exposed part of the composition to the dissolution rate of theunexposed part of the composition. As a result, a pattern with a highdegree of resolution can be obtained. By using the quinone diazidecompound, it becomes possible to produce a positive-workingphotosensitivity resin composition which can be photosensitized with iline (365 nm), h line (405 nm) and g line (436 nm) of a conventionalmercury lamp. These photo-acid generators may be used singly, or two ormore of them may be used in combination. In either case, ahigh-sensitivity photosensitive resin composition can be produced.

In the present invention, as the quinone diazide, a quinone diazidehaving a 5-naphthoquinone diazide sulfonyl group is preferably used. Theabsorption of a naphthoquinone diazide sulfonyl ester compound extendsto a g line range of a mercury lamp, and is therefore suitable for theexposure to g line and the exposure to light within the whole wavelengthrange.

The molecular weight of the quinone diazide compound is preferably 300or more, more preferably 350 or more, and is preferably 3000 or less,more preferably 1500 or less, from the viewpoint of the heat resistance,mechanical properties and bonding properties of a film produced by aheat treatment. The content of the quinone diazide compound ispreferably 1 part by weight or more, more preferably 3 parts by weightor more, and is preferably 50 parts by weight or less, more preferably40 parts by weight or less, relative to 100 parts by weight of (A) thealkali-soluble resin. When the content is 1 to 50 parts by weight, itbecomes possible to impart photosensitiveness to a film produced after aheat treatment while maintaining the heat resistance, chemicalresistance and mechanical properties of the film.

Among these photo-acid generators, a sulfonium salt, a phosphonium saltand a diazonium salt are preferred, because an acid component generatedupon the exposure to light can be stabilized appropriately.Particularly, a sulfonium salt is preferred.

The content of the sulfonium salt, the phosphonium salt or the diazoniumsalt is preferably 0.5 to 20 parts by weight relative to 100 parts byweight of (A) the alkali-soluble resin, from the viewpoint of increasingsensitivity. In addition, a sensitizer or the like may be contained, ifnecessary.

The resin composition according to the present invention contains (D) asolvent. Specific examples of the solvent to be used in the presentinvention include: a polar aprotic solvent, such asN-methyl-2-pyrrolidone, gamma-butyrolactone, N,N-dimethylformamide,N,N-dimethylacetamide and dimethyl sulfoxide; an ether, such astetrahydrofuran, dioxane and propylene glycol monomethyl ether; aketone, such as acetone, methyl ethyl ketone, diisobutyl ketone anddiacetone alcohol; an ester, such as ethyl acetate, propylene glycolmonomethyl ether acetate and ethyl lactate; and an aromatic hydrocarbon,such as toluene and xylene. These solvents may be used singly, or two ormore of them may be used in combination.

The content of the solvent to be used in the present invention ispreferably 50 parts by weight or more, more preferably 100 parts byweight or more, and is preferably 2000 parts by weight or less, morepreferably 1500 parts by weight or less, relative to 100 parts by weightof (A) the alkali-soluble resin.

It is preferred that the resin composition according to the presentinvention contains (J) a compound which does not have an absorptionmaximum at a wavelength of 340 nm or more and less than 436 nm and hasan absorption maximum at a wavelength of 436 to 750 nm inclusive. As thecompound, a thermally color-developing compound, or a dye and/or anorganic pigment can be used preferably. At least one type of thecomponent (J) may be contained. For example, a method in which one typeof thermally color-developing compound or one type of dye or organicpigment is used, a method in which a mixture of at least two thermallycolor-developing compound or dye or organic pigment is used, and amethod in which at least one type of thermally color-developingcompound, at least one type of dye and at least one type of organicpigment are used in combination can be mentioned. In the presentinvention, a method in which a compound having an absorption maximum ata wavelength of 436 to 750 nm is used is preferably selected.

The thermally color-developing compound which can be used as thecomponent (J) in the present invention preferably has a color-developingtemperature of 120° C. or higher, preferably 150° C. or higher. The heatresistance under high-temperature conditions becomes superior with theincrease in the color-developing temperature of the thermallycolor-developing compound, and the thermally color-developing compoundrarely undergoes discoloration upon the irradiation with ultravioletlight or visible light for a long period and therefore has excellentlight resistance.

The organic pigment to be used as the component (J) in the presentinvention is preferably a pigment having high heat resistance and lightresistance. The dye to be used as the compound for the component (J) ispreferably a dye which is soluble in an organic solvent that candissolve (A) the alkali-soluble resin and is compatible with the resin.The dye may also be a dye having high heat resistance and high lightresistance.

The component (J) to be used in the resin composition according to thepresent invention preferably contains (J1) a dye and/or an organicpigment each having an absorption maximum at a wavelength of 436 nm ormore and less than 490 nm.

The dye to be used as the component (J1) in the present invention ispreferably: a dye which is soluble in an organic solvent that candissolve (A1) the polyimide, the polybenzoxazole, the polyimideprecursor or the polybenzoxazole precursor or (A2) the resin having sucha backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, and which iscompatible with the resin; or a dye having high heat resistance and highlight resistance, from the viewpoint of storage stability anddiscoloration upon curing or irradiation with light. The component (J1)has an absorption maximum at a wavelength of 436 nm or more and lessthan 490 nm, and specific examples thereof include a yellow dye and anorange dye. The type of the dye includes an oil-soluble dye, adispersible dye, a reactive dye, an acidic dye, a direct dye and thelike.

Examples of the backbone structure of the dye include, but not limitedto, those of an anthraquinone-type, an azo-type, a phthalocyanine-type,a methine-type, an oxazine-type, a quinoline-type, atriarylmethane-type, and a xanthene-type. Among these backbonestructures, backbone structures of an anthraquinone-type, an azo-type, amethine-type, a triarylmethane-type and a xanthene-type are preferred,from the viewpoint of the solubility in an organic solvent and heatresistance. These dyes may be used singly or may be used in the form ofa metal-containing complex salt. Specific examples thereof include, butare not limited to, Sumilan and Lanyl dyes (manufactured by SumitomoChemical Co., Ltd.); Orasol, Oracet, Filamid, and Irgasperse dyes(manufactured by Ciba Specialty Chemicals Inc.); Zapon, Neozapon,Neptune, and Acidol dyes (manufactured by BASF Corporation); Kayaset andKayakalan dyes (manufactured by Nippon Kayaku Co., Ltd.); Valifastcolors dye (manufactured by Orient Chemical Industries, Ltd.); Savinyl,Sandoplast, Polysynthren, and Lanasyn dyes (manufactured by ClariantJapan Co., Ltd.); Aizen Spilon dye (manufactured by Hodogaya ChemicalCo., Ltd.); functional dye (manufactured by Yamada Chemical Co., Ltd.);and Plast Color dye, and Oil Color dye (manufactured by Arimoto ChemicalCo., Ltd.). These dyes may be used singly, or a mixture of two or moreof them may be used.

The organic pigment to be used as the component (J1) in the presentinvention is preferably a pigment having high heat resistance and lightresistance, from the viewpoint of discoloration during curing orirradiation with light.

Specific examples of the organic pigment to be used are mentioned interms of color index (CI) numbers as follows. Specific examples of theyellow pigment include pigment yellow 83, 117, 129, 138, 139, 150 and180. Specific examples of the orange pigment include pigment orange 38,43, 64, 71 and 72. A pigment other than the above-mentioned pigments mayalso be used.

The content of the component (J1) to be used in the present invention ispreferably 0.1 to 300 parts by weight, more preferably 0.2 to 200 partsby weight, particularly preferably 1 to 200 parts by weight, relative to100 parts by weight of (A1) the polyimide, the polybenzoxazole, thepolyimide precursor or the polybenzoxazole precursor or (A2) the resinhaving such a backbone structure that two cyclic structures are bondedto a cyclic-structure-constituting quaternary carbon atom. When thecontent of the component (J1) is 0.1 part by weight or more, it becomespossible to absorb light having a wavelength corresponding to thepigment. When the content is 300 parts by weight or less, it becomespossible to absorb light having a wavelength corresponding to thepigment while maintaining the adhesion strength between a photosensitivecolor resin film and a substrate and also maintaining the heatresistance and mechanical properties of a film after a heat treatment.

In the present invention, the organic pigment to be used as thecomponent (J1) may be subjected to a surface treatment, such as a rosintreatment, an acidic group treatment and a basic group treatment, ifnecessary. The organic pigment may also be used together with adispersant optionally. Examples of the dispersant include a cationicsurfactant, an anionic surfactant, a nonionic surfactant, an amphotericsurfactant, a silicone-type surfactant and a fluorine-containingsurfactant.

The component (J) to be used in the resin composition according to thepresent invention preferably contains (J2) a dye and/or an organicpigment each having an absorption maximum at a wavelength of 490 nm ormore and less than 580 nm.

The dye to be used as the component (J2) in the present invention ispreferably: a dye which is soluble in an organic solvent that candissolve (A1) the polyimide, the polybenzoxazole, the polyimideprecursor or the polybenzoxazole precursor or (A2) the resin having sucha backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, and which iscompatible with the resin; or a dye having high heat resistance and highlight resistance, from the viewpoint of storage stability anddiscoloration upon curing or irradiation with light. The component (J2)has an absorption maximum at a wavelength of 490 nm or more and lessthan 580 nm, and examples thereof include a red dye and a violet dye.

The type of the dye includes an oil-soluble dye, a dispersible dye, areactive dye, an acidic dye, a direct dye and the like.

Examples of the backbone structure of the dye include, but not limitedto, those of an anthraquinone-type, an azo-type, a phthalocyanine-type,a methine-type, an oxazine-type, a quinoline-type, atriarylmethane-type, and a xanthene-type. Among these backbonestructures, backbone structures of an anthraquinone-type, an azo-type, amethine-type, a triarylmethane-type and a xanthene-type are preferred,from the viewpoint of the solubility in an organic solvent and heatresistance. These dyes may be used singly or may be used in the form ofa metal-containing complex salt. Specific examples thereof include, butare not limited to, Sumilan and Lanyl dyes (manufactured by SumitomoChemical Co., Ltd.); Orasol, Oracet, Filamid, and Irgasperse dyes(manufactured by Ciba Specialty Chemicals Inc.); Zapon, Neozapon,Neptune, and Acidol dyes (manufactured by BASF Corporation); Kayaset andKayakalan dyes (manufactured by Nippon Kayaku Co., Ltd.); Valifastcolors dye (manufactured by Orient Chemical Industries, Ltd.); Savinyl,Sandoplast, Polysynthren, and Lanasyn dyes (manufactured by ClariantJapan Co., Ltd.); Aizen Spilon dye (manufactured by Hodogaya ChemicalCo., Ltd.); functional dye (manufactured by Yamada Chemical Co., Ltd.);and Plast Color dye, and Oil Color dye (manufactured by Arimoto ChemicalCo., Ltd.). These dyes may be used singly, or a mixture of two or moreof them may be used.

The organic pigment to be used as the component (J2) in the presentinvention is preferably a pigment having high heat resistance and lightresistance, from the viewpoint of discoloration during curing orirradiation with light.

Specific examples of the organic pigment to be used are mentioned interms of color index (CI) numbers as follows. Specific examples of thered pigment include pigment red 48:1, 122, 168, 177, 202, 206, 207, 209,224, 242 and 254. Specific examples of the violet pigment includepigment violet 19, 23, 29, 32, 33, 36, 37 and 38. A pigment other thanthe above-mentioned pigments may also be used.

The content of the component (J2) to be used in the present invention ispreferably 0.1 to 300 parts by weight, more preferably 0.2 to 200 partsby weight, particularly preferably 1 to 200 parts by weight, relative to100 parts by weight of (A1) the polyimide, the polybenzoxazole, thepolyimide precursor or the polybenzoxazole precursor or (A2) the resinhaving such a backbone structure that two cyclic structures are bondedto a cyclic-structure-constituting quaternary carbon atom. When thecontent of the component (J2) is 0.1 part by weight or more, it becomespossible to absorb light having a wavelength corresponding to thepigment. When the content is 300 parts by weight or less, it becomespossible to absorb light having a wavelength corresponding to thepigment while maintaining the adhesion strength between a.photosensitive color resin film and a substrate and the heat resistanceand mechanical properties of a film after a heat treatment.

In the present invention, the organic pigment to be used as thecomponent (J2) may be subjected to a surface treatment, such as a rosintreatment, an acidic group treatment and a basic group treatment, ifnecessary. The organic pigment may also be used together with adispersant, if necessary. Examples of the dispersant include a cationicsurfactant, an anionic surfactant, a nonionic surfactant, an amphotericsurfactant, a silicone-type surfactant and a fluorine-containingsurfactant.

The component (J) to be used in the resin composition according to thepresent invention preferably contains (J3) a dye and/or a pigment havingan absorption maximum at a wavelength of 580 nm or more and less than750 nm.

The dye to be used as the component (J3) in the present invention ispreferably a dye which is soluble in an organic solvent that candissolve (A1) the polyimide, the polybenzoxazole, the polyimideprecursor or the polybenzoxazole precursor or (A2) the resin having sucha backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, and which iscompatible with the resin, or a dye having high heat resistance and highlight resistance, from the viewpoint of storage stability anddiscoloration upon curing or irradiation with light. The component (J3)has an absorption maximum at a wavelength of 580 nm or more and lessthan 750 nm, and examples thereof include a blue dye and a green dye.

The type of the dye includes an oil-soluble dye, a dispersible dye, areactive dye, an acidic dye, a direct dye and the like.

Examples of the backbone structure of the dye include, but not limitedto, those of an anthraquinone-type, an azo-type, a phthalocyanine-type,a methine-type, an oxazine-type, a quinoline-type, atriarylmethane-type, and a xanthene-type. Among these backbonestructures, backbone structures of an anthraquinone-type, an azo-type, amethine-type, a triarylmethane-type and a xanthene-type are preferred,from the viewpoint of the solubility in an organic solvent and heatresistance. These dyes may be used singly or may be used in the form ofa metal-containing complex salt. Specific examples thereof include, butare not limited to, Sumilan and Lanyl dyes (manufactured by SumitomoChemical Co., Ltd.); Orasol, Oracet, Filamid, and Irgasperse dyes(manufactured by Ciba Specialty Chemicals Inc.); Zapon, Neozapon,Neptune, and Acidol dyes (manufactured by BASF Corporation); Kayaset andKayakalan dyes (manufactured by Nippon Kayaku Co., Ltd.); Valifastcolors dye (manufactured by Orient Chemical Industries, Ltd.); Savinyl,Sandoplast, Polysynthren, and Lanasyn dyes (manufactured by ClariantJapan Co., Ltd.); Aizen Spilon dye (manufactured by Hodogaya ChemicalCo., Ltd.); functional dye (manufactured by Yamada Chemical Co., Ltd.);and Plast Color dye, and Oil Color dye (manufactured by Arimoto ChemicalCo., Ltd.). These dyes may be used singly, or a mixture of two or moreof them may be used.

The organic pigment to be used as the component (J3) in the presentinvention is preferably a pigment having high heat resistance and lightresistance, from the viewpoint of discoloration during curing orirradiation with light.

Specific examples of the organic pigment to be used are mentioned interms of color index (CI) numbers as follows. Specific examples of theblue pigment include pigment blue 15 (e.g., 15:3, 15:4, 15:6), 21, 22,60 and 64. Specific examples of the green pigment include pigment green7, 10, 36, 47 and 58. A pigment other than the above-mentioned pigmentsmay also be used.

The content of the component (J3) to be used in the present invention ispreferably 0.1 to 300 parts by weight, more preferably 0.2 to 200 partsby weight, particularly preferably 1 to 200 parts by weight, relative to100 parts by weight of (A1) the polyimide, the polybenzoxazole, thepolyimide precursor or the polybenzoxazole precursor or (A2) the resinhaving such a backbone structure that two cyclic structures are bondedto a cyclic-structure-constituting quaternary carbon atom. When thecontent of the component (J3) is 0.1 part by weight or more, it becomespossible to absorb light having a wavelength corresponding to thepigment. When the content is 300 parts by weight or less, it becomespossible to absorb light having a wavelength corresponding to thepigment while maintaining the adhesion strength between a photosensitivecolor resin film and a substrate and the heat resistance and mechanicalproperties of a film after a heat treatment.

In the present invention, the organic pigment to be used as thecomponent (J3) may be subjected to a surface treatment, such as a rosintreatment, an acidic group treatment and a basic group treatment, ifnecessary. The organic pigment may also be used together with adispersant, if necessary. Examples of the dispersant include a cationicsurfactant, an anionic surfactant, a nonionic surfactant, an amphotericsurfactant, a silicone-type surfactant and a fluorine-containingsurfactant.

In the present invention, the film can be blackened by additionallyusing the components (J1), (J2) and (J3). The degree of blackening canbe expressed by an optical density (an OD value), and the OD value ispreferably 0.15 or more, more preferably 0.4 or more, still morepreferably 1.0 or more.

The resin composition according to the present invention mayadditionally contain (F) a compound having 3 to 6 thermallycrosslinkable groups per molecule. When the component (F) is contained,it becomes possible to impart positive-working photosensitivity andimprove the chemical resistance of the heat-resistant resin film.

As the component (F), a compound represented by general formula (4) or acompound having a structure represented by general formula (5) ispreferred.

In general formula (4) above, R²⁶ represents a bivalent to tetravalentlinking group. R²⁷ represents Cl, Br, I, F, a monovalent hydrocarbongroup having 1 to 20 carbon atoms, a group having such a structure that—CH₂— in a monovalent hydrocarbon group having 1 to 20 carbon atoms issubstituted by —CO—, —COO—, —NH—, —NHCO—, —O—, —S—, —SO₂—, —Si— or—Si(CH₃)₂—, or a group having such a structure that a hydrogen atom in amonovalent hydrocarbon group having 1 to 20 carbon atoms is substitutedby a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitrogroup, a cyano group, a fluorine atom, a chlorine atom or —COOR³¹. R³¹represents a hydrogen atom or an alkyl group having 1 to 20 carbonatoms. R²⁸ and R²⁹ independently represent CH₂OR³² that is a thermallycrosslinkable group. R³² represents a hydrogen atom or a monovalenthydrocarbon group having 1 to 6 carbon atoms. R³⁰ represents a hydrogenatom, a methyl group or an ethyl group. R³² is preferably a monovalenthydrocarbon group having 1 to 4 carbon atoms, because proper reactivitycan still remain and excellent storage stability can be achieved. In aphotosensitive resin composition containing a photo-acid generator andthe like, R³² is more preferably a methyl group or an ethyl group. trepresents an integer of 0 to 2, and u represents an integer of 2 to 4.The multiple R²⁷'s, R²⁸'s, R²⁹'s and R³⁰'s may be the same as ordifferent from one another. Specific examples of the linking group R²⁶are as follows.

In the formula, R³³ to R⁵³ independently represent a hydrogen atom, Cl,Br, I, F, a monovalent hydrocarbon group having 1 to 20 carbon atoms, agroup having such a structure that —CH₂— in a monovalent hydrocarbongroup having 1 to 20 carbon atoms is substituted by —CO—, —COO—, —NH—,—NHCO—, —O—, —S—, —SO₂—, —Si— or —Si(CH₃)₂—, or a group having such astructure that a hydrogen atom in a monovalent hydrocarbon group having1 to 20 carbon atoms is substituted by a fluoroalkyl group, a hydroxylgroup, an alkoxyl group, a nitro group, a cyano group, a fluorine atom,a chlorine atom, or —COOR⁵⁴. R⁵⁴ represents a hydrogen atom or an alkylgroup having 1 to 20 carbon atoms.

—N(CH₂OR⁵⁵)_(v)(H)_(w)  (5)

In general formula (5), R⁵⁵ represents a hydrogen atom or a monovalenthydrocarbon group having 1 to 6 carbon atoms. v represents 1 or 2, and wrepresents 0 or 1, wherein v+w is 1 or 2.

The purity of the compound having a structure represented by generalformula (4) is preferably 75% or more, more preferably 85% or more. Whenthe purity is 85% or more, it becomes possible to achieve excellentstorage stability, to perform the crosslinking reaction of the resincomposition satisfactorily to achieve excellent coloring propertiesafter curing, and to further decrease the transmittance of theheat-resistant resin film to light having a wavelength within a visiblelight range. In addition, it also becomes possible to reduce the numberof unreacted groups that act as water-absorbable groups, resulting inthe decrease in water absorbability of the resin composition. As themethod for producing a high-purity thermal crosslinking agent, methodssuch as recrystallization and distillation can be mentioned. The purityof the thermal crosslinking agent can be determined by a liquidchromatography method.

Preferred examples of the compound having a structure represented bygeneral formula (4) are as follows.

Preferred examples of the crosslinking agent having a structurerepresented by general formula (5) are as follows.

In the present invention, an epoxy compound is also preferred as thecomponent (F). Examples of the epoxy compound include, but are notlimited to, TEPIC (registered trademark) S, TEPIC (registered trademark)G, and TEPIC (registered trademark) P (trade names, manufactured byNISSAN CHEMICAL INDUSTRIES, LTD.), DENACOL (registered trademark)EX-321L (trade name, manufactured by Nagase ChemteX Corporation),VG3101L (trade name, manufactured by Printec Co.), EPPN 502H and NC3000(trade names, manufactured by Nippon Kayaku Co., Ltd.), and EPICLON(registered trademark) N695 and HP-7200 (trade names, manufactured byDIC CORPORATION).

In the present invention, these components (F) may be used singly, ortwo or more of them may be used in combination.

The content of the component (F) is preferably 5 parts by weight ormore, more preferably 10 parts by weight or more, and is preferably 120parts by weight or less, more preferably 100 parts by weight or less,relative to 100 parts by weight of (A) the alkali-soluble resin. Whenthe content is 5 to 120 parts by weight inclusive, the strength of theheat-resistant resin film is increased and the storage stability of theresin composition becomes excellent.

The resin composition according to the present invention mayadditionally contain (G) a compound having a phenolic hydroxyl group.Because the compound can compensate alkali developability, it becomespossible to impart positive-working photosensitivity.

Examples of the compound having a phenolic hydroxyl group include, butare not limited to, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA,TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ,BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X,DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X,DML-EP, DML-POP, dimethylol-BisOC-P, DMLPFP, DML-PSBP, DML-MTrisPC,TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP,HML-TPPHBA, HML-TPHAP (trade names, manufactured by Honshu ChemicalIndustry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP,BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (tradenames, manufactured by ASAHI YUKIZAI CORPORATION),2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol,2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methylgallate, bisphenol A, bisphenol E, methylene bisphenol, and BisP-AP(trade name, manufactured by Honshu Chemical Industry Co., Ltd.).

In the present invention, the content of the component (G) is preferably3 to 50 parts by weight inclusive relative to 100 parts by weight of (A)the alkali-soluble resin.

The resin composition according to the present invention mayadditionally contain (H) a thermal acid generator. The thermal acidgenerator can generate an acid upon a heat treatment after developmentas mentioned below to accelerate the crosslinking reaction between (A)the alkali-soluble resin and the component (F) (i.e., the thermalcrosslinking agent), and also accelerate the cyclization of an imidering or an oxazole ring in (A) the alkali-soluble resin such as apolyimide precursor or a polybenzoxazole precursor. As a result, thechemical resistance of the heat-resistant resin film can be improved andthe thinning of the film can be prevented. The acid generated from thethermal acid generator is preferably a strong acid, and is preferably,for example, an arylsulfonic acid such as p-toluenesulfonic acid andbenzene sulfonic acid, and an alkylsulfonic acid such as methanesulfonicacid, ethanesulfonic acid and butanesulfonic acid. In the presentinvention, the thermal acid generator is preferably any one of aliphaticsulfonic acid compounds each represented by general formula (6) or (7).Two or more of these compounds may be contained.

In general formulae (6) and (7), R⁵⁶ to R⁵⁸ independently represent analkyl group having 1 to 10 carbon atoms or a monovalent aromatic grouphaving 7 to 12 carbon atoms. In the alkyl group and the aromatic group,at least one hydrogen atom may be substituted. Specific examples of thesubstituent include an alkyl group and a carbonyl group.

Specific examples of the compound represented by general formula (6) areas follows.

Specific examples of the compound represented by general formula (7) areas follows.

The content of the thermal acid generator (H) is preferably 0.1 part byweight or more, more preferably 0.3 part by weight or more, still morepreferably 0.5 part by weight or more, relative to 100 parts by weightof (A) the alkali-soluble resin, from the viewpoint of furtheraccelerating the crosslinking reaction. On the other hand, the contentis preferably 20 parts by weight or less, more preferably 15 parts byweight or less, still more preferably 10 parts by weight or less, fromthe viewpoint of the electrical insulation properties of theheat-resistant resin film.

The resin composition according to the present invention may alsocontain an adhesion-improving agent. Examples of the adhesion-improvingagent include silane coupling agents such as vinyl trimethoxysilane,vinyl triethoxysilane, epoxy cyclohexyl ethyl trimethoxysilane,3-glycidoxy propyl trimethoxysilane, 3-glycidoxy propyl triethoxysilane,p-styryl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyltriethoxysilane, and N-phenyl-3-aminopropyl trimethoxysilane, titaniumchelate agents, aluminum chelate agents, and compounds obtained byreacting a aromatic amine compound with an alkoxy group-containingsilicon compound. Two or more of these adhesion-improving agents may becontained. When the adhesion-improving agent is contained, it becomespossible to enhance the close adhesion to an underlying base material,e.g., a silicon wafer, ITO, SiO₂ and nitride silicon, during thedevelopment of a photosensitive resin film. It becomes also possible toenhance the resistance to oxygen plasma, which is used for washingpurposes or the like, or an UV ozone treatment. The content of theadhesion-improving agent is preferably 0.1 to 10 parts by weightrelative to 100 parts by weight of (A) the alkali-soluble resin.

The resin composition according to the present invention may alsocontain a bonding-improving agent. Specific examples of thebonding-improving agent include an alkoxysilane-containing aromaticamine compound, an aromatic amide compound, and a silane compoundcontaining no aromatic moiety. Two or more of these bonding-improvingagents may be contained. When the compound is contained, it becomespossible to improve the bonding to a base material after burning orcuring. Specific examples of the alkoxysilane-containing aromatic aminecompound and the aromatic amide compound are shown below. In addition tothese compounds, a compound produced by reacting an aromatic aminecompound with an alkoxy-group-containing silicon compound may also beused. A specific example of the compound is a compound produced byreacting an aromatic amine compound with an alkoxysilane compound havinga group capable of reacting with an amino group such as an epoxy groupor a chloromethyl group.

Examples of the silane compound containing no aromatic moiety includevinyl silane compounds such as vinyl trimethoxysilane, vinyltriethoxysilane, vinyl trichlorosilane, and vinyltris(β-methoxyethoxy)silane, and carbon-carbon unsaturatedbond-containing silane compounds such as 3-methacryloxy propyltrimethoxysilane, 3-acryloxy propyl trimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxy propyl methyl dimethoxysilane, and3-methacryloxy propyl methyl diethoxysilane. Among these compounds,vinyltrimethoxysilane and vinyltriethoxysilane are preferred.

The content of the bonding-improving agent is preferably 0.01 to 15parts by weight relative to 100 parts by weight of (A) thealkali-soluble resin.

A compound which can act as both of an adhesion-improving agent and abonding-improving agent, such as vinyltrimethoxysilane andvinyltriethoxysilane, may also be contained.

The resin composition according to the present invention may contain asurfactant to improve the wettability with a substrate.

Specific examples of the surfactant include: a fluorine-containingsurfactant, such as Florad (a product name, manufactured by Sumitomo 3MInc.), Megaface (a product name, manufactured by DIC Corporation) andSurflon (a product name, manufactured by Asahi Glass Co., Ltd.); anorganic siloxane surfactant, such as KP341 (a product name, manufacturedby Shin-Etsu Chemical Co., Ltd.), DBE (a product name, manufactured byChisso Corporation), Glanol (a product name, manufactured by KyoeishaChemical Co., Ltd.) and BYK (manufactured by BYK-Chemie); and an acrylicpolymer surfactant, such as Polyflow (a product name, manufactured byKyoeisha Chemical Co., Ltd.).

Next, the method for producing the resin composition according to thepresent invention will be described. The positive-working photosensitiveresin composition can be produced by, for example, dissolving thecomponents (A), (D) and (I), the component (C), and optionally thecomponents (E), (H), the adhesion-improving agent, the bonding-improvingagent, the surfactant and the like. Examples of the method for thedissolution include stirring and heating. When heating is employed, itis preferred to adjust the heating temperature to a temperature fallingwithin a range at which the performance of the positive-workingphotosensitive resin composition cannot be deteriorated, and the heatingtemperature is generally room temperature to 80° C. The order ofdissolution of the components is not particularly limited. For example,a method can be mentioned, in which the compounds are dissolved in orderof increasing solubility. With respect to a component that is likely togenerate bubbles during stirring or dissolution, such as surfactants andsome types of adhesion-improving agents, the component can be addedfinally after all of the other components are dissolved, therebypreventing the insufficient dissolution of the other components due tothe generation of the bubbles.

It is preferred that the resin composition thus produced is filteredthrough a filtration filter to remove foreign matters and particles. Thefilter pore size is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm or0.02 μm, but is not limited thereto. Specific examples of the materialfor the filtration filter include polypropylene (PP), polyethylene (PE),nylon (NY) and polytetrafluoroethylene (PTFE), and polyethylene andnylon are preferred. In the case where an organic pigment is containedin the resin composition, it is preferred to use a filtration filterhaving a larger pore size than the particle diameters of the organicpigment.

Next, the method for producing the heat-resistant resin film using theresin composition according to the present invention will be described.The resin composition according to the present invention is applied by aspin coating method, a slit coating method, a dip coating method, aspray coating method, a printing method or the like to produce a coatingfilm of the resin composition. Prior to the application, a base materialonto which the resin composition is to be applied may be pre-treatedwith the above-mentioned adhesion-improving agent. For example, a methodcan be mentioned, in which the surface of the base material is treatedby, for example, spin coating, slit die coating, bar coating, dipcoating, spray coating or a treatment with steam using a solutionprepared by dissolving the adhesion-improving agent in a solvent, suchas isopropanol, ethanol, methanol, water, tetrahydrofuran, propyleneglycol monomethyl ether acetate, propylene glycol monomethyl ether,ethyl lactate and diethyl adipate, at a concentration of 0.5 to 20% byweight. If necessary, it is possible to carry out a drying treatmentunder reduced pressure and then carry out a heat treatment at 50 to 300°C. to allow the reaction of the base material with theadhesion-improving agent to proceed the reaction between the basematerial and the adhesion-improving agent.

Subsequently, the coating film of the resin composition is dried toproduce a photosensitive resin film. It is preferred to carry out thedrying at 50 to 150° C. for 1 minute to several hours with an oven, ahot plate, infrared ray or the like.

Subsequently, an actinic ray is emitted over the photosensitive resinfilm through a mask having a desired pattern. Examples of the actinicray to be used for the light exposure include ultraviolet ray, visibleray, electron beam and X-ray. In the present invention, it is preferredto use i line (365 nm), h line (405 nm) or g line (436 nm) of a mercurylamp.

Subsequently, the photosensitive resin film that has been exposed tolight is developed to remove an exposed region. A developing solution ispreferably an aqueous solution of a compound having alkalinity, such astetramethylammonium, diethanolamine, diethylaminoethanol, sodiumhydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,triethylamine, diethylamine, methylamine, dimethylamine,dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethylmethacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine.If necessary, at least one component selected from a polar solvent suchas N-methyl-2-pyrrolidone, N,N-dimethylfoimamide, N,N-dimethylacetamide,dimethyl sulfoxide, γ-butyrolactone and dimethylacrylamide, an alcoholsuch as methanol, ethanol and isopropanol, an ester such as ethyllactate and propylene glycol monomethyl ether acetate and a ketone suchas cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutylketone may be added to the aqueous alkaline solution. After thedevelopment, a rinsing treatment with water is generally carried out.The rinsing treatment may be carried out using a solution prepared byadding an alcohol, e.g., ethanol and isopropyl alcohol, or an ester,e.g., ethyl lactate and propylene glycol monomethyl ether acetate, towater.

The photosensitive resin film thus produced is subjected to a heattreatment to produce a heat-resistant resin film. The term “heattreatment” as used herein refers to a treatment by heating at atemperature falling within the range from 200 to 350° C. For example, amethod in which the heat treatment is carried out at 250° C. for 60minutes can be mentioned. The heating treatment may be carried out undera nitrogen atmosphere or in air.

The heat-resistant resin film produced from the resin compositionaccording to the present invention can be used suitably as an insulatingfilm or a protective film for wiring lines. For example, theheat-resistant resin film can be used as an insulating film or aprotective film for wiring lines made from copper, aluminum or the likein a printed substrate produced by forming the wiring lines on a film orsubstrate made from polyimide, ceramic or the like, or as a protectivefilm for use in partial soldering of the wiring lines. In the case wherethe resin composition contains an electrically conductive filler, theheat-resistant resin film can also be used as a wiring material.

The heat-resistant resin film produced from the resin compositionaccording to the present invention can also be used suitably as aplanarization film in a display device equipped with a substrate havingTFTs formed thereon, the planarization film and display elements in thisorder. Examples of the display device having this configuration includea liquid crystal display device and an organic EL display device. Anactive-matrix-type display device has such a configuration that: TFTsand wiring lines which are respectively positioned on the side of theTFTs and which are connected to the TFTs are arranged on a glass- orplastic-made substrate; a planarization film is arranged on the wiringlines and the TFTs in such a manner as to cover projections anddepressions on the wiring lines and the TFTs; and display elements arearranged on the planarization film. The display elements and the wiringlines are connected to each other through contact holes formed in theplanarization film. In FIG. 1, the cross-sectional view of a TFTsubstrate is illustrated. Bottom-gate-type or top-gate-type TFTs 1 areprovided in a matrix shape on a substrate 6, an insulating film 3 isformed in such a manner as to cover the TFTs 1. Wiring lines 2, whichare respectively connected to the TFTs 1, are provided on the insulatingfilm 3. A planarization film 4 is also provided on the insulating film 3in such a manner that the wiring lines 2 are embedded in theplanarization film 4. Contact holes 7, which reach the wiring lines 2,are formed in the planarization film 4. ITOs (transparent electrodes) 5are formed on the planarization film 4 in such a manner that the ITOs 5are connected to the wiring lines 2 respectively through the contactholes 7. The ITOs 5 serve as electrodes for display elements (e.g.,organic EL elements). The organic EL elements may be of atop-emission-type which can emit luminescent light from a side opposedto the substrate 6 or a bottom-emission-type from which light can beextracted from the substrate 6 side, and is preferably of atop-emission-type. In this manner, an active-matrix-type organic ELdisplay device, in which TFTs 1 for driving organic EL elements areconnected to the organic EL elements, is produced.

In the case of an organic EL display device using TFTs in each of whicha semiconductor layer is made from amorphous silicon, microcrystalsilicon, a metal oxide (e.g., IGZO) or the like, there may be caseswhere an undesirable phenomenon, such as the deterioration ormalfunctions of the device, the development of a leakage current in thedevice or the like, is caused as the result of the penetration of lighthaving a relatively high energy, e.g., ultraviolet light or visiblelight in a short wavelength range. The heat-resistant resin filmproduced from the resin composition according to the present inventionhas an absorption at a wavelength of 340 to 450 nm. Therefore, in theorganic EL display device equipped with the heat-resistant resin film,the deterioration or malfunctions of the device, the development of aleakage current in the device or the like can be prevented and stabledriving/luminous properties can be achieved in the device.

An organic EL display device using TFTs, in each of which asemiconductor layer is made from a metal oxide, is particularlypreferably a high-resolution device. The degree of resolution ispreferably 100 ppi or more, more preferably 200 ppi or more. When theheat-resistant resin film produced from the positive-workingphotosensitive resin composition according to the present invention isused in the high-resolution organic EL device, it becomes possible tomore efficiently prevent the occurrence of an undesirable phenomenon,such as the deterioration or malfunctions of the device or thedevelopment of a leakage current in the device which can be caused bythe penetration of light.

In addition, the heat-resistant resin film produced from the resincomposition according to the present invention can be used suitably as:a surface protective film or an interlayer insulating film forsemiconductor devices including LSIs; a bonding agent or an underfillingagent to be used in the packaging of devices; a capping agent forpreventing the migration of copper; a planarization film for on-chipmicrolenses for solid-state imaging elements and various types ofdisplays and solid-state imaging elements; and others.

EXAMPLES

First, the invention according to the first aspect will be describedbyway of examples. However, the present invention is not limited bythese examples. The evaluations of the resin compositions in theexamples were carried out by the methods mentioned below.

(1) Evaluation of Light Transmittance of Resin Composition

A resin composition (referred to as a “varnish”, hereinafter) wasspin-coated on a 5-cm-square glass substrate in such a manner that thefilm thickness of the resultant film after a heat treatment became 2.0μm, and the film was prebaked at 120° C. for 2 minutes. Subsequently,the film was cured under an air atmosphere at 250° C. for 60 minutesusing a high-temperature clean oven CLH-21CD(V)-S (manufactured by KoyoThermo Systems Co., Ltd.) to produce a heat-resistant resin film. Thefilm thickness of the heat-resistant resin film was measured usingSURFCOM 1400D (manufactured by Tokyo Seimitsu Co., Ltd.) under theassumption that the refractive index was 1.629. The prebaked film andthe cured film thus produced were measured with respect to transmissionspectra in a wavelength range of 300 to 800 nm using an ultraviolet andvisible spectrophotometer “MultiSpec-1500” (manufactured by ShimadzuCorporation). A prebaked film having such a result that a lighttransmittance at a wavelength of 365 to 436 nm was less than 50% wasrated as “insufficient (C)”, and a prebaked film having such a resultthat a light transmittance at a wavelength of 365 to 436 nm was 50% ormore was rated as “good (A)”. A cured film having such a result that alight transmittance at a wavelength of 350 to 460 nm was more than 5%was rated as “insufficient (C)”, a cured film having such a result thata light transmittance at a wavelength of 350 to 460 nm was 5% or lesswas rated as “good (A)”, and a cured film having such a result that alight transmittance at a wavelength of 350 to 460 nm was 4% or less wasrated as “extremely good (S)”. When the heat-resistant resin film doesnot have a thickness of 2.0 μm after a heat treatment, the lighttransmittance of the heat-resistant resin film can be determined byconverting the thickness of the measured heat-resistant resin film to2.0 μm in accordance with the Lambert's law, and the transmissionspectra were determined with respect to the heat-resistant resin filmhaving a thickness of 2.0 μm.

(2) Evaluation of Sensitivity

A varnish produced in each of Examples and Comparative Examples wasspin-coated on an 8-inch-square silicon wafer, and then the varnish wassubjected to a heat treatment (prebaking) at 120° C. for 2 minutes usinga hot plate (a coater/developer “Act-8”, manufactured by Tokyo ElectronLimited) to produce a prebaked film. The prebaked film was exposed tolight at a light exposure amount of 0 to 1000 mJ/cm² at steps of 20mJ/cm² using an i line stepper (NSR-2005i9C, manufactured by NikonCorporation) or a mask aligner (PEM-6M, manufactured by Union OpticalCo., LTD.). Line & space (L&S) patterns were as follows: 1, 2, 3, 4, 5,6, 7, 8, 9, 10, 15, 20, 30, 50 and 100 μm. After the exposure to light,the resultant film was developed with a 2.38-wt % aqueoustetramethylammonium (TMAH) solution (manufactured by Tama Chemicals Co.,Ltd.) for 30 to 100 seconds, and was then rinsed with purified water toform a relief pattern. The film thicknesses after the prebaking and thedevelopment were measured using an interferometer type film thicknessmeasurement system Lambda Ace STM-602 (manufactured by Dainippon ScreenManufacturing Co. Ltd.) under the assumption that the refractive indexwas 1.629.

After the exposure to light and the development, the smallest lightexposure amount at which a line & space (L & S) pattern of 50 μm wasformed at a ratio of 1:1 was employed as a value of the sensitivity.

(3) Evaluation of Surface Roughing of Film after Development

A pattern was formed in the section (2) above, and then the occurrenceof roughing on the surface in a 5-um hole after the development wasconfirmed using a field emission-type scanning X-ray analyzer (S-4800,manufactured by Hitachi Ltd.). A film in which the roughing of thesurface was observed was rated as “insufficient (C)”, and a film inwhich the roughing of the surface was not observed was rated as “good(A)”.

(Synthesis Example 1) Synthesis of Hydroxyl-Group-Containing DiamineCompound

2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured byCentral Glass Co., Ltd., abbreviated as “BAHF”, hereinafter) (18.3 g)(0.05 mole) was dissolved in acetone (100 mL) and propylene oxide(manufactured by Tokyo Chemical Industry Co., Ltd.) (17.4 g) (0.3 mole),and the resultant mixture was cooled to −15° C. To the resultantsolution was dropwisely added a solution prepared by dissolving3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co.,Ltd.) (20.4 g) (0.11 mole) in acetone (100 mL). After the completion ofthe dropwise addition, the resultant solution was stirred at −15° C. for4 hours and then warmed to room temperature. A precipitated white solidmaterial was filtered off and then dried in vacuo at 50° C.

The white solid material thus produced (30 g) was introduced into a300-mL stainless autoclave and was then dispersed in methyl cellosolve(250 mL), and then 5% palladium-carbon (manufactured by Wako PureChemical Industries, Ltd.) (2 g) was added thereto. Hydrogen wasintroduced into the reaction solution with a balloon to perform areduction reaction at room temperature. After about 2 hours, it wasconfirmed that the balloon could not shrink any more, and the reactionwas terminated. After the completion of the reaction, the reactionsolution was filtered to remove the palladium compound that was acatalyst, and then the filtrate was concentrated with a rotaryevaporator to produce a hydroxyl-group-containing diamine compoundrepresented by the following formula.

(Synthesis Example 2) Synthesis of Polyamic Acid Ester (A1-1)

Under a dry nitrogen stream, the hydroxyl-group-containing diamine (57.4g) (0.095 mole) produced in Synthesis Example 1 and1,3-bis(3-aminopropyl)tetramethyldisiloxane (abbreviated as “SiDA”,hereinafter) (1.24 g) (0.005 mole) were dissolved in NMP (200 g).4,4′-Oxydiphthalic anhydride (abbreviated as “ODPA”, hereinafter) (31.0g) (0.1 mole) was added to the solution, and the resultant solution wasstirred at 40° C. for 2 hours. Subsequently, a solution prepared bydiluting dimethylformamide dimethyl acetal (manufactured by MitsubishiRayon Co., Ltd., abbreviated as “DFA”, hereinafter) (7.14 g) (0.06 mole)with NMP (5 g) was dropwisely added to the solution over 10 minutes.After the dropwise addition, the stirring of the resultant solution wascontinued 40° C. for 2 hours. After the completion of the stirring, thesolution was introduced into water (2 L), and then precipitates of apolymer solid material were collected by filtration. The precipitateswere further washed with water (2 L) three times, and then the collectedpolymer solid material was dried with a vacuum drier at 50° C. for 72hours to produce a polyamic acid ester (A1-1).

(Synthesis Example 3) Synthesis of Resin Having Such Backbone Structurethat Two Cyclic Structures are Bonded to Cyclic-Structure-ConstitutingQuaternary Carbon Atom (A2-1)

Under a dry nitrogen stream, into a four-necked flask equipped with areflux condenser were charged a 50% PGMEA solution of an equalequivalent reaction product of a bisphenol fluorene-type epoxy resinwith acrylic acid (manufactured by Nippon Steel Chemical Co., Ltd.,product name “ASF-400” solution) (198.53 g), benzophenonetetracarboxylicdianhydride (39.54 g) (0.12 mole), succinic anhydride (8.13 g) (0.08mole), PGMEA (48.12 g) and triphenylphosphine (0.45 g). The resultantmixture was stirred under heating at 120 to 125° C. for 1 hour and thenfurther stirred under heating at 75 to 80° C. for 6 hours. Subsequently,glycidyl methacrylate (8.6 g) was introduced into the reaction solution,and the resultant solution was further stirred at 80° C. for 8 hours toproduce a resin having such a backbone structure that two cyclicstructures are bonded to a cyclic-structure-constituting quaternarycarbon atom (A2-1).

(Synthesis Example 4) Synthesis of Phenolic Resin (A3-1)

Under a dry nitrogen stream, m-cresol (70.2 g) (0.65 mole), p-cresol(37.8 g) (0.35 mole), a 37 wt % aqueous formaldehyde solution (75.5 g)(formaldehyde 0.93 mole), oxalic acid dihydrate (0.63 g) (0.005 mole)and methyl isobutyl ketone (264 g) were charged into a flask, and then apolycondensation reaction was carried out for 4 hours while immersingthe flask in an oil bath and while refluxing the reaction solution.Subsequently, the temperature of the oil bath was raised over 3 hours,then the inner pressure of the flask was reduced to 40 to 67 hPa toremove a volatile component, and then the reaction solution was cooledto room temperature to produce a polymer solid material of a phenolicresin (A3-1). The weight average molecular weight of the polymer solidmaterial as measured by GPC was 3500.

(Synthesis Example 5) Synthesis of Phenolic Resin (A3-2)

Under a dry nitrogen stream, phenol (94 g) (1 mole), a 37% aqueousformaldehyde solution (243.3 g) (3 moles) and a 10% sodium hydroxideaqueous solution (80 g) (0.2 mole) were charged into a flask and theresultant solution was reacted at 40° C. for 8 hours. Subsequently, thereaction solution was heated to 80° C. and was then further reacted at80° C. for 10 hours. After the completion of the reaction, the reactionsolution was cooled, and then a 15% aqueous sulfuric acid solution wasadded slowly thereto to adjust the pH to 3.0.

At this point of time, the reaction product was separated into a lowerlayer, i.e., a resol-type phenolic resin intermediate, and an upperlayer, i.e., an aqueous layer portion containing a neutralization salt,a phenol monomer and a mononucleic methylolated phenol. The upper layersolution was removed, then water (300 g) was added to and mixed with thelower layer solution, then the resultant solution was allowed to standto cause separation, and then the upper layer solution was removed. To acontent solution produced by carrying out a dehydration treatment in thesystem were added 1-butanol (296 g) (4 moles) and 75% phosphoric acid(13 g) (0.2 mole). The inner temperature was raised under ambientpressure until reflux was initiated, and then an alkoxylation reactionwas carried at 115 to 123° C. for 3 hours. During this reaction, for thepurpose of completing the reaction, the reaction was continued whilecontinuously removing water generated during the reaction. After thecompletion of this 3-hour reaction, toluene (552 g) (6 moles) was addedto the reaction solution, then ion-exchanged water (300 g) was addedthereto, and then the solution was agitated and was then allowed tostand.

The reaction product was separated into an upper layer resin solution,which contained a resol-type phenolic resin in which a terminal methylolgroup was butyletherated, and a lower layer aqueous solution, whichcontained phosphoric acid that was used as a catalyst in thealkoxylation reaction. The lower layer solution was removed, then water(300 g) was added to and mixed with the upper layer solution, then theresultant solution was allowed to stand to cause separation, and thenthe lower layer solution was removed in the same manner as mentionedabove. This procedure was repeated until the metal content in the systemwas reduced to 1 ppm or less, and the solvent was removed under areduced pressure, GBL was added thereto to adjust the non-volatilecomponent to 50% in the solution. The solution was a phenolic resin(A3-2). The phenolic resin (A3-2) had a weight average molecular weightof 5800 and a degree of alkoxylation of 80%.

(Synthesis Example 6) Synthesis of Polyhydroxystyrene Resin (A3-3)

Under a dry nitrogen stream, p-t-butoxystyrene and styrene were added ata molar ratio of 3:1 in a total amount of 20 g to a mixed solution oftetrahydrofuran (500 ml) and sec-butyllithium (0.01 mole) that served asan initiator, and then the resultant solution was polymerized for 3hours while stirring. A polymerization termination reaction was carriedout by adding methanol (0.1 mole) to the reaction solution.Subsequently, for the purpose of purifying a polymer, the reactionmixture was poured into methanol to precipitate a polymer. Theprecipitated polymer was dried to produce a white polymer. The whitepolymer was dissolved in acetone (400 ml), then a small volume ofconcentrated hydrochloric acid was added thereto at 60° C., and theresultant solution was stirred for 7 hours and then poured into water toprecipitate a polymer. p-t-Butoxystyrene in the polymer was deprotectedto convert it to hydroxystyrene, and then the product was washed andthen dried to produce a purified polyhydroxystyrene resin (A3-3). Theweight average molecular weight as measured by GPC was 3500.

(Synthesis Example 7) Synthesis of Polyhydroxystyrene Resin (A3-4)

To a solution prepared by dissolving sodium hydroxide (80 g) (2.0 moles)in purified water (800 g) was dissolved the polyhydroxystyrene resin(A-5) produced in Synthesis Example 6. After being dissolved completely,a 36 to 38 wt % aqueous formalin solution (686 g) was dropwisely addedto the solution at 20 to 25° C. over 2 hours. Subsequently, theresultant solution was stirred at 20 to 25° C. for 17 hours. Sulfuricacid (98 g) and water (552 g) were added to the solution to neutralizethe solution, and the neutralized solution was allowed to stand for 2days. A white solid material formed in the solution after the allowingto stand was washed with water (100 mL). The white solid material wasdried in vacuo at 50° C. for 48 hours.

Subsequently, the compound thus produced was dissolved in methanol (300mL), then sulfuric acid (2 g) was added to the solution, and theresultant solution was stirred at room temperature for 24 hours. Ananion-type ion exchange resin (AMBERLYST IRA96SB, manufactured byRohmand Haas Company) (15 g) was added to the solution, the resultantsolution was stirred for 1 hour, and then the ion exchange resin wasremoved by filtration. Subsequently, gamma-butyrolactone (500 mL) wasadded to the solution, and methanol was removed from the solution with arotary evaporator to produce a gamma-butyrolactone solution. The resinwas analyzed by NMR (GX-270, manufactured by JOEL Ltd.), and it wasfound that a partly alkoxylated polyhydroxystyrene resin (A3-4) wasproduced. The product (A3-4) was analyzed by GPC, and it was found thatthe product had a weight average molecular weight (Mw) of 8000 (in termsof GPC polystyrene) and contained an alkoxylated hydroxystyrene moietyat an introduction rate of 35 mol % per 1 mole of hydroxystyrene.

(Synthesis Example 8) Synthesis of Quinone Diazide Compound (C-1)

Under a dry nitrogen stream,4,4′-[1-[4-[1-(4-hydroxyphenyl-1)-1-methylethyl]phenyl]ethylidene]bisphenol(manufactured by Honshu Chemical Industry Co., Ltd., abbreviated as“TrisP-PA”, hereinafter) (21.22 g) (0.05 mole) and5-naphthoquinonediazidesulfonic acid chloride (NAC-5, manufactured byToyo Gosei Co., Ltd) (26.8 g) (0.1 mole) were dissolved in 1,4-dioxane(450 g) and the temperature of the solution was adjusted to roomtemperature. Triethylamine (12.65 g) that was mixed with 1, 4-dioxane(50 g) was dropwisely added to the solution in such a manner that thetemperature in the system did not become 35° C. or higher. After thedropwise addition, the solution was stirred at 40° C. for 2 hours. Atriethylamine salt was filtered off, and a filtrate was introduced intowater. Subsequently, precipitates were collected by filtration and thenwashed with 1% aqueous hydrochloric acid (1 L). Subsequently, the washedproduct was further washed with water (2 L) two times. The precipitateswere dried with a vacuum drier to produce a quinone diazide compound(C-1) represented by the following formula.

Example 1

The polyamic acid ester (A1-1) (10 g) produced in Synthesis Example 2,the phenolic resin (A3-1) (3 g) produced in Synthesis Example 4 and4,4′,4″,4′″-(1,4-phenylenedimethylidene)tetrakisphenol (maximumabsorption wavelength: 440 nm) (3.5 g) that was a thermallycolor-developing compound were weighed and then dissolved inγ-butyrolactone (abbreviated as “GBL”, hereinafter) (50 g) to produce avarnish of a polyimide precursor composition. The transmittance wasmeasured using the varnish, and the transmittance at a wavelength within365 to 436 nm before a heat treatment was 50% or more. The transmittanceat a wavelength within 350 to 460 nm after the heat treatment was 4.2%or less.

(Examples 2 to 6), (Comparative Examples 1 to 7)

Varnishes were produced in the same procedure as in Example 1, exceptthat the types and amounts of the compounds were as shown in Tables 1and 3. Each of the varnishes was used to measure transmittances beforeand after a heat treatment. The evaluation results are shown in Tables 2and 4.

TABLE 1 Components of resin composition Component Solvent (A1, A2)Component (A3) Component (B) Component (C) (D) (content) (content)(content) (content) (content) Example 1 Polyamic acid ester Phenolicresin (A3-1) 4,4′,4″,4′″-(1,4- — GBL (A1-1) (3 g)phenylenedimethylidene)tetrakisphenol (absorption (50 g) (10 g) maximumwavelength: 440 nm) (3.5 g) Example 2 Polyamic acid ester Phenolic resin(A3-1) 4,4′,4″-methylidenetrisphenol — GBL (A1-1) (3 g) (absorptionmaximum wavelength: 460 nm) (50 g) (10 g) (3.5 g) Example 3 Polyamicacid ester Polyhydroxystyrene 4,4′,4″-methylidenetrisphenol — GBL (A1-1)resin (A3-3) (absorption maximum wavelength: 460 nm) (50 g) (10 g) (3 g)(3.5 g) Example 4 Cardo resin (A2-1) Phenolic resin (A3-1)4,4′,4″-methylidenetrisphenol (absorption maximum — GBL (10 g) (3 g)wavelength: 460 nm) (50 g) (3.5 g) Example 5 Polyamic acid esterPhenolic resin (A3-2) 4,4′,4″-methylidenetrisphenol (absorption maximum— GBL (A1-1) (3 g) wavelength: 460 nm) (50 g) (10 g) (3.5 g) Example 6Polyamic acid ester Polyhydroxystyrene 4,4′,4″-methylidenetrisphenol(absorption maximum — GBL (A1-1) resin (A3-4) wavelength: 460 nm) (50 g)(10 g) (3 g) (3.5 g)

TABLE 2 Light transmittance properties Light transmittance (%) atwavelength Light transmittance (%) at within 365-436 nm wavelengthwithin 350-460 nm before heat treatment after heat treatment Example 1 A(≧50%) A (≦4.2%) Example 2 A (≧50%) A (≦4.3%) Example 3 A (≧50%) A(≦4.5%) Example 4 A (≧50%) A (≦4.3%) Example 5 A (≧50%) A (≦4.9%)Example 6 A (≧50%) A (≦4.9%)

TABLE 3 Components of resin composition Component Component ComponentComponent Solvent (A1, A2) (A3) (B) (C) (D) Others (content) (content)(content) (content) (content) (content) Comparative Polyamic —4,4′,4″-methyl- — GBL — Example 1 acid ester idenetrisphenol (50 g)(A1-1) (10 g) (absorption maximum wavelength: 460 nm) (3.5 g)Comparative — Phenolic resin — — GBL — Example 2 (A3-1) (10 g) (50 g)Comparative — Polyhydroxy- — — GBL — Example 3 styrene resin (50 g)(A3-3) (10 g) Comparative Polyamic — 4,4′,4″-methyl- — GBL Tinuvin ®Carboprotect Example 4 acid ester idenetrisphenol (50 g) (absorptionmaximum (A1-1) (10 g) (absorption maximum wavelength: 378 nm)wavelength: 460 nm) (2 g) (3.5 g) Comparative Cardo resin —4,4′,4″-methyl- — GBL — Example 5 (A2-1) (10 g) idenetrisphenol (50 g)(absorption maximum wavelength: 460 nm) (3.5 g) Comparative — Phenolicresin — — GBL — Example 6 (A3-2) (10 g) (50 g) Comparative —Polyhydroxy- — — GBL — Example 7 styrene resin (50 g) (A3-4) (10 g)

TABLE 4 Light transmittance properties Light transmittance Lighttransmittance (%) (%) at wavelength at wavelength within within 365-436nm before heat 350-460 nm treatment after heat treatment Comparative A(≧50%) C (>5.0% in some range) Example 1 Comparative A (≧50%) C (>5.0%in some range) Example 2 Comparative A (≧50%) C (>5.0% in some range)Example 3 Comparative C (≦50% in some range) A (≦4.3%) Example 4Comparative A (≧50%) C (>5.0% in some range) Example 5 Comparative A(≧50%) C (>5.0% in some range) Example 6 Comparative A (≧50%) C (>5.0%in some range) Example 7

In Each of Example 2 to 6 which were resin compositions each contained(A1) a polyimide, a polybenzoxazole, a polyimide precursor or apolybenzoxazole precursor or (A2) a resin having such a backbonestructure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, (A3) a phenolicresin and/or a polyhydroxystyrene resin, (B) a thermallycolor-developing compound and (D) a solvent, wherein the component (A3)was contained in an amount of 5 to 50 parts by weight inclusive relativeto 100 parts by weight of the component (A1), the transmittance at awavelength within the range from 365 to 436 nm before the heat treatmentwas 50% or more. In each of Example 2 to 6, the transmittance at awavelength within the range from 350 to 460 nm after the heat treatmentwas 5.0% or less. In each of Comparative Examples 1 to 2 in which thecomponent (A3) was not contained and Comparative Examples 3 to 6 inwhich the component (A1) and the component (B) were not contained, thetransmittance at a wavelength within the range from 365 to 436 nm beforethe heat treatment was 50% or more. However, the transmittance at awavelength within the range from 350 to 460 nm after the heat treatmentwas higher than 5.0% in some range. In Comparative Example 7 in which acompound having a maximum absorption wavelength of 378 nm was contained,the transmittance at a wavelength within the range from 365 to 436 nmbefore the heat treatment was lower than 50%.

Example 7

A polyamic acid ester (A1-1) (10 g), a phenolic resin (A3-1) (3 g),4,4′,4″,4′″-(1,4-phenylenedimethylidene)tetrakisphenol (maximumabsorption wavelength: 440 nm) (3.5 g) which was a thermallycolor-developing compound and the quinone diazide compound (C-1) (4.0 g)produced in Synthesis Example 8 were weighed and then dissolved in GBL(50 g) to produce a varnish of a polyimide precursor composition. Thevarnish was used to evaluate photosensitiveness, and the sensitivity was120 mJ/cm². The formation of scums was not observed after thedevelopment. The transmittance at a wavelength within the range from 350to 460 nm after the heat treatment was 4.2% or less.

Examples 8 to 27, Comparative Examples 8 to 17

Varnishes were produced in the same procedure as in Example 7, exceptthat the types and amounts of the compounds were as shown in Tables 5-1,5-2 and 7. The names and the structures of the compounds shown in Tables5-1 and 5-2 are as follows.

Component (F): HMOM-TPHAP (product name, manufactured by Honshu ChemicalIndustry Co., Ltd.)

Each of the varnishes was used to evaluate photosensitive and measuretransmittances before and after a heat treatment. The evaluation resultsare shown in Tables 6 and 8.

TABLE 5 Components of resin composition Component Component ComponentComponent Solvent (A1, A2) (A3) (B) (C) (D) Others (content) (content)(content) (content) (content) (content) Example 7 Polyamic Phenolicresin 4,4′,4″,4″′-(1,4-phenylene- quinonediazide GBL — acid aster (A3-1)(3 g) dimethylidene)tetrakisphenol compound (50 g) (A1-1) (10 g)(absorption maximum (C-1) (4 g) wavelength: 440 nm) (3.5 g) Example 8Polyamic Phenolic resin 4-[bis (4-hydroxy- quinonediazide GBL — acidester (A3-1) (3 g) phenyl)methyl]- compound (50 g) (A1-1) (10 g)2-methoxyphenol (C-1) (4 g) (absorption maximum wavelength: 470 nm) (3.5g) Example 9 Polyamic Phenolic resin 4,4′,4″-methyl- quinonediazide GBL— acid ester (A3-1) (3 g) idenetrisphenol compound (50 g) (A1-1) (10 g)(absorption maximum (C-1) (4 g) wavelength: 460 nm) (3.5 g) Example 10Polyamic Polyhydroxy- 4,4′,4″-methyl- quinonediazide GBL — acid esterstyrene resin idenetrisphenol compound (50 g) (A1-1) (10 g) (A3-1) (3 g)(absorption maximum (C-1) (4 g) wavelength: 460 nm) (3.5 g) Example 11Polyamic Phenolic resin 4,4′,4″-methyl- quinonediazide GBL Oil Yellow5001 acid ester (A3-1) (3 g) idenetrisphenol compound (50 g) (absorptionmaximum (A1-1) (10 g) (absorption maximum (C-1) (4 g) wavelength: 480nm) wavelength: 460 nm) (1.5 g) (2.5 g) Example 12 Polyamic Phenolicresin 4,4′,4″-methyl- quinonediazide GBL — acid aster (A3-1) (1 g)idenetrisphenol compound (50 g) (A1-1) (10 g) (absorption maximum (C-1)(4 g) wavelength: 460 nm) (3.5 g) Example 13 Polyamic Phenolic resin4,4′,4″-methyl- quinonediazide GBL — acid ester (A3-1) (4 g)idenetrisphenol compound (50 g) (A1-1) (10 g) (absorption maximum (C-1)(4 g) wavelength: 46D nm) (3.5 g) Example 14 Polyamic Phenolic resin4,4′,4″-methyl- quinonediazide GBL — acid ester (A3-1) (2 g)idenetrisphenol compound (50 g) (A1-1) (10 g) Polyhydroxy- (absorptionmaximum (C-1) (4 g) styrene resin wavelength: 460 nm) (A3-3) (2 g) (3.5g) Example 15 Polyamic Phenolic resin 4,4′,4″-methyl- quinonediazide GBLValifast Red 3311 acid ester (A3-1) (3 g) idenetrisphenol compound (50g) (absorption maximum (A1-1) (10 g) (absorption maximum (C-1) (4 g)wavelength: 525 nm) wavelength: 460 nm) (2.5 g) (3.5 g) Valifast Blue2620 (absorption maximum wavelength: 690 nm) (2.5 g) Example 16 PolyamicPhenolic resin 4,4′,4″-methyl- quinonediazide GBL Plast Red 8380 acidester (A3-1) (3 g) idenetrisphenol compound (50 g) (absorption maximum(A1-1) (10 g) (absorption maximum (C-1) (4 g) wavelength: 550 nm, 590nm) wavelength: 460 nm) (3 g) (3.5 g) Plast Blue DB463 (absorptionmaximum wavelength: 590 nm, 630 nm) (3.5 g) Example 17 Cardo resinPhenolic resin 4,4′,4″-methyl- quinonediazide GBL — (A2-1) (10 g) (A3-1)(3 g) idenetrisphenol compound (50 g) (absorption maximum (C-1) (4 g)wavelength: 460 nm) (3.5 g) Example 18 Polyamic Phenolic resin4,4′,4″-methyl- quinonediazide GBL (F)HMOM-TPHAP acid ester (A3-1) (3 g)idenetrisphenol compound (50 g) (1.5 g) (A1-1) (10 g) (absorptionmaximum (C-1) (4 g) wavelength: 460 nm) (3.5 g) Example 19 PolyamicPhenolic resin 4,4′,4″-methyl- quinonediazide GBL — acid ester (A3-2) (3g) idenetrisphenol compound (50 g) (A1-1) (10 g) (absorption maximum(C-1) (4 g) wavelength: 460 nm) (3.5 g) Example 20 Polyamic Polyhydroxy-4,4′,4″-methyl- quinonediazide GBL — acid ester styrene resinidenetrisphenol compound (50 g) (A1-1) (10 g) (A3-4) (3 g) (absorptionmaximum (C-1) (4 g) wavelength: 460 nm) (3.5 g) Example 21 PolyamicPhenolic resin 4,4′,4″-methyl- quinonediazide GBL (E)Plast Yellow 8070acid ester (A3-2) (3 g) idenetrisphenol compound (50 g) (absorptionmaximum (A1-1) (10 g) (absorption maximum (C-1) (4 g) wavelength: 445nm) wavelength: 460 nm) (1.5 g) (2.5 g) Example 22 Polyamic Polyhydroxy-4,4′,4″-methyl- quinonediazide GBL (E)Plast Yellow 8070 acid estersytrene resin idenetrisphenol compound (50 g) (absorption maximum (A1-1)(10 g) (A3-3) (3 g) (absorption maximum (C-1) (4 g) wavelength: 445 nm)wavelength: 460 nm) (1.5 g) (2.5 g) Example 23 Polyamic Polyhydroxy-4,4′,4″-methyl- quinonediazide GBL (E)Plast Yellow 8070 acid esterstyrene resin idenetrisphenol compound (50 g) (absorption maximum (A1-1)(10 g) (A3-4) (3 g) (absorption maximum (C-1) (4 g) wavelength: 445 nm)wavelength: 460 nm) (1.5 g) (2.5 g) Example 24 Polyamic Phenolic resin4,4′,4″-methyl- quinonediazide GBL (E)Plast Yellow 8070 acid ester(A3-1) (3 g) idenetrisphenol compound (50 g) (absorption maximum (A1-1)(10 g) (absorption maximum (C-1) (4 g) wavelength: 445 nm) wavelength:460 nm) (1.5 g) (3.5 g) Valifast Red 3311 (absorption maximumwavelength: 525 nm) (1.5 g) Valifast Blue 2620 (absorption maximumwavelength: 690 nm) (2.0 g) Example 25 Polyamic Phenolic resin4,4′,4″-methyl- quinonediazide GBL (E)Plast Yellow 8070 acid ester(A3-2) (3 g) idenetrisphenol compound (50 g) (absorption maximum (A1-1)(10 g) (absorption maximum (C-1) (4 g) wavelength: 445 nm) wavelength:460 nm) (1.5 g) (3.5 g) Valifast Red 3311 (absorption maximumwavelength: 525 nm) (1.5 g) Valifast Blue 2620 (absorption maximumwavelength: 690 nm) (2.0 g) Example 26 Polyamic Polyhydroxy-4,4′,4″-methyl- quinonediazide GBL (E)Plast Yellow 8070 acid esterstyrene resin idenetrisphenol compound (50 g) (absorption maximum (A1-1)(10 g) (A3-3) (3 g) (absorption maximum (C-1) (4 g) wavelength: 445 nm)wavelength: 460 nm) (1.5 g) (3.5 g) Valifast Red 3311 (absorptionmaximum wavelength: 525 nm) (1.5 g) VAlifAst Blue 2620 (absorptionmaximum wavelength: 690 nm) (2.0 g) Example 27 Polyamic Polyhydroxy-4,4′,4″-methyl- quinonediazide GBL (E)Plast Yellow 8070 acid esterstyrene resin idenetrisphenol compound (50 g) (absorption maximum (A1-1)(10 g) (A3-4) (3 g) (absorption maximum (C-1) (4 g) wavelength: 445 nm)wevelength: 460 nm) (1.5 g) (3.5 g) Valifast Red 3311 (absorptionmaximum wavelength: 525 nm) (1.5 g) Valifast Blue 2620 (absorptionmaximum wavelength: 690 nm) (2.0 g)

TABLE 6 Post-development properties Post-heat treatment propertiesSensitivity Light transmittance (%) at (i line) Surface roughnesswavelength (mJ/cm²) after development within 350-460 nm Example 7 120 AA (≦4.2%) Example 8 120 A A (≦4.5%) Example 9 90 A A (≦4.3%) Example 90A A (≦4.4%) 10 Example 120 A S (≦3.9%) 11 Example 100 A A (≦4.8%) 12Example 80 A S (≦3.4%) 13 Example 90 A S (≦3.7%) 14 Example 400 A A(≦4.6%) 15 Example 200 A A (≦4.7%) 16 Example 120 A A (≦4.3%) 17 Example90 A A (≦4.5%) 18 Example 90 A A (≦4.9%) 19 Example 90 A A (≦4.9%) 20Example 120 A A (≦4.6%) 21 Example 120 A S (≦3.9%) 22 Example 120 A A(≦4.7%) 23 Example 200 A S (≦3.7%) 24 Example 200 A A (≦4.4%) 25 Example200 A S (≦3.8%) 26 Example 200 A A (≦4.5%) 27

TABLE 7 Components of resin composition Component Component ComponentComponent Solvent (A1, A2) (A3) (B) (C) (D) Others (content) (content)(content) (content) (content) (content) Comparative Polyamic —4,4′,4″-methyl- quinonediazide GBL — Example 8 acid esteridenetrisphenol compound (50 g) (A1-1) (10 g) (absorption maximum (C-1)(4 g) wavelength: 460 nm) (3.5 g) Comparative — Phenolic resin —quinonediazide GBL — Example 9 (A3-1) (10 g) compound (50 g) (C-1) (4 g)Comparative — Polyhydroxy- — quinonediazide GBL — Example 10 styreneresin compound (50 g) (A3-3) (10 g) (C-1) (4 g) Comparative Polyamic —4,4′,4″-methyl- quinonediazide GBL Valifast Red 3311 Example 11 acidester idenetrisphenol compound (50 g) (absorption maximum (A1-1) (10 g)(absorption maximum (C-1) (4 g) wavelength: 525 nm) wavelength: 460 nm)(3 g) (3.5 g) Valifast Blue 2620 (absorption maximum wavelength: 690 nm)(3 g) Comparative Polyamic — 4,4′,4″-methyl- quinonediazide GBLTinuvin ® Carboprotect Example 12 acid ester idenetrisphenol compound(50 g) (absorption maximum (A1-1) (10 g) (absorption maximum (C-1) (4 g)wavelength: 378 nm) wavelength: 460 nm) (2 g) (3.5 g) ComparativePolyamic Phenolic resin 4,4′,4″-methyl- quinonediazide GBL — Example 13acid ester (A3-1) idenetrisphenol compound (50 g) (A1-1) (5.5 g)(absorption maximum (C-1) (4 g) (10 g) wavelength: 460 nm) (3.5 g)Comparative Polyamic Phenolic resin 4,4′,4″-methyl- quinonediazide GBL —Example 14 acid ester (A3-1) (10 g) idenetrisphenol compound (50 g)(A1-1) (10 g) (absorption maximum (C-1) (4 g) wavelength: 460 nm) (3.5g) Coraparative Cardo resin — 4,4′,4″-methyl- quinonediazide GBL —Example 15 (A2-1) (10 g) idenetrisphenol compound (50 g) (absorptionmaximum (C-1) (4 g) wavelength: 460 nm) (3.5 g) Comparative — Phenolicresin — quinonediazide GBL — Example 16 (A3-2) (10 g) compound (50 g)(C-1) (4 g) Comparative — Polyhydroxy- — quinonediazide GBL — Example 17styrene resin compound (50 g) (A3-4) (10 g) (C-1) (4 g)

TABLE 8 Post-development properties Post-heat treatment propertiesSensitivity Surface Light transmittance (%) at (i line) roughness afterwavelength (mJ/cm²) development within 350-460 nm Comparative 90 A C(>5.0% in some range) Example 8 Comparative 90 A C (>5.0% in some range)Example 9 Comparative 90 A C (>5.0% in some range) Example 10Comparative 400 A C (>5.0% in some range) Example 11 Comparative >1000 AA (≦4.3%) Example 12 Comparative 80 C S (≦3.5%) Example 13 Comparative80 C S (≦3.2%) Example 14 Comparative 110 A C (>5.0% in some range)Example 15 Comparative 90 A C (>5.0% in some range) Example 16Comparative 90 A C (>5.0% in some range) Example 17

In each of Examples 7 to 14, 17 to 23 which were resin compositions eachcontaining (A1) a polyimide, a polybenzoxazole, a polyimide precursor ora polybenzoxazole precursor or (A2) a resin having such a backbonestructure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, (A3) a phenolicresin and/or a polyhydroxystyrene resin, (B) a thermallycolor-developing compound, (C) a photo-acid generator, (D) a solvent andother component wherein the component (A3) was contained in an amount of5 to 50 parts by weight inclusive relative to 100 parts by weight of thecomponent (A1), and having positive-working photosensitivity, thesensitivity was 120 mJ/cm² or less. The formation of scums after thedevelopment was not observed. The transmittance at a wavelength withinthe range from 350 to 460 nm after the heat treatment was 5.0% or less.In each of Example 15, 16, 24 to 27 in each of which a combination oftwo or three types of dyes having different maximum absorptionwavelengths from one another was used as a dye component that served asthe component (E), the sensitivity was 400 mJ/cm² or less. The formationof scums after the heat treatment was not observed. The transmittance ata wavelength within the range from 350 to 460 nm after the heattreatment was 5.0% or less. Because of the use of a combination of thethree types of dyes having different maximum absorption wavelengths fromone another, the finished products were blackened and the OD values were0.5 or less.

In each of Comparative Examples 8, 11 to 12, 15 in each of which thecomponent (A3) was not contained and Comparative Examples 9 to 10 and 16to 17 in each of which the component (A1) and the component (B) were notcontained, the transmittance after the heat treatment was higher than 5%in some range. In Comparative Example 12 in which the compound having amaximum absorption wavelength of 378 nm was contained, light having thesame wavelength as that of exposing light was absorbed by the compoundhaving a maximum absorption wavelength of 378 nm and therefore thesensitivity was deteriorated. In Comparative Examples 13 to 14 in eachof which the amount of the phenolic resin (A3) was larger than 50 partsby weight relative to 100 parts by weight of the component (A1), theformation of scums was observed during development.

Example 28

Bottom-gate-type oxide TFTs, which were designed in such a manner as tohave a resolution of 200 ppi, were formed on a glass substrate, and thenan insulating film made from Si₃N₄ was formed in such a manner as tocover the TFTs. Subsequently, contact holes were formed in theinsulating film, and then wiring lines (height: 1.0 μm), which were tobe connected to the TFTs through the contact holes, were formed on theinsulating film. The wiring lines were intended to connect the TFTs toeach other or to connect the TFTs to organic EL elements which wereformed in the latter step.

Subsequently, in order to planarize projections and depressions producedas the result of the formation of the wiring lines, a planarization filmwas formed on the insulating film in such a manner as to fill theprojections and depressions produced as the result of the formation ofthe wiring lines. The formation of the planarization film on theinsulating film was carried out by spin-coating a varnish of aphotosensitive polyimide precursor compositions produced in each ofExamples 7 to 27 onto a substrate, then prebaking the varnish on a hotplate at 120° C. for 2 minutes, and then subjecting the prebaked film toa heat treatment at 250° C. for 60 minutes. The coatability during theapplication of the varnish was good, and wrinkling or cracking did notoccur in a heat-resistant resin film produced after the exposure tolight, development and burning. The average difference in level of thewiring lines was 500 nm, and the film thickness of the planarizationfilm was 2000 nm.

The photodeterioration upon the irradiation of oxide TFT devices, eachhaving the planarization film provided therein, with light under theapplication of negative stress was measured. The occurrence of change ina threshold voltage (the shift of a threshold value) before and afterthe irradiation with light was prevented, and therefore aphotodeterioration prevention effect was confirmed.

Example 29

Bottom-gate-type oxide TFTs, which were designed in such a manner as tohave a resolution of 200 ppi, were formed on a glass substrate, and thenan insulating film made from Si₃N₄ was formed in such a manner as tocover the TFTs. Subsequently, contact holes were formed in theinsulating film, and then wiring lines (height: 1.0 μm), which were tobe connected to the TFTs through the contact holes, were formed on theinsulating film. The wiring lines were intended to connect the TFTs toeach other or to connect the TFTs to organic EL elements which wereformed in the latter step.

Subsequently, in order to planarize projections and depressions producedas the result of the formation of the wiring lines, a planarization filmwas formed on the insulating film in such a manner as to fill theprojections and depressions produced as the result of the formation ofthe wiring lines. The formation of the planarization film on theinsulating film was carried out by spin-coating a varnish of aphotosensitive polyimide precursor compositions produced in each ofExamples 7 to 27 onto a substrate, then prebaking the varnish on a hotplate at 120° C. for 2 minutes, and then subjecting the prebaked film toa heat treatment at 250° C. for 60 minutes. The coatability during theapplication of the varnish was good, and wrinkling or cracking did notoccur in a heat-resistant resin film produced after the exposure tolight, development and burning. The average difference in level of thewiring lines was 500 nm, and the film thickness of the planarizationfilm was 2000 nm.

Subsequently, top-emission-type organic EL elements were formed on theplanarization film. First, bottom electrodes each made from ITO wereformed on the planarization film by sputtering in such a manner as to beconnected to the wiring lines through the contact holes. Subsequently, aresist was applied and then prebaked, then light was emitted over theprebaked product through a mask having a desired pattern, and then thelight-exposed product was developed. A pattern processing was carriedout using the resist pattern as a mask by wet etching using an ITOetchant. Subsequently, the resist pattern was stripped with a resiststripping solution (a mixed solution of monoethanolamine and DMSO(dimethyl sulfoxide)). The bottom electrodes thus produced correspond toanodes for the organic EL elements.

Subsequently, an insulating layer having such a shape as to cover theperipheries of the bottom electrodes was formed. For the material of theinsulating layer, a varnish of a photosensitive polyimide precursorcomposition produced in each of Examples 7 to 27 was used. When theinsulating layer is provided, it becomes possible to prevent theoccurrence of short out between the bottom electrode and an upperelectrode that were formed in the latter step. The insulating layer waspatterned, and was then subjected to a heat treatment at 250° C. for 60minutes to form an insulating layer.

Subsequently, a hole-transport layer, a red organic light-emittinglayer, a green organic light-emitting layer, a blue organiclight-emitting layer and an electron-transport layer were formed in thisorder by deposition through a desired pattern mask in a vacuumevaporator. Subsequently, an upper electrode made from Al was formedover the whole area of the upper surface of the substrate. The upperelectrode corresponds to a cathode of the organic EL elements. Thesubstrate thus produced was removed from the evaporator, and was thensealed by adhering to a glass substrate for sealing use using anultraviolet-ray-curable epoxy resin.

In this manner, an active-matrix-type organic EL display device, inwhich TFTs for driving organic EL elements were connected to the organicEL elements, was produced. When a voltage was applied to the devicethrough a driving circuit, good emission of light was observed.

Next, the invention according to the second aspect will be described byway of examples. However, the present invention is not limited by theseexamples. The evaluations of the resin compositions in the examples werecarried out by the methods mentioned below.

(1) Measurement of Maximum Absorption Wavelength of (I) Compound WhoseMaximum Absorption Wavelength Shifts by Heat Treatment

The component (I) was dissolved in gamma-butyrolactone, and theabsorption was measured using a spectrophotometer MultiSpec-150(manufactured by Shimadzu Corporation).

(2) Evaluation of Light Transmittance of Resin Composition

A resin composition (referred to as a “varnish”, hereinafter) wasspin-coated on a 5-cm-square glass substrate in such a manner that thefilm thickness of the resultant film after a heat treatment became 3.0μm, and the film was prebaked at 120° C. for 2 minutes. Subsequently,the film was cured under nitrogen stream (oxygen concentration: 20 ppmor less) at 250° C. for 60 minutes using a high-temperature clean ovenCLH-21CD(V)-S (manufactured by Koyo Thermo Systems Co., Ltd.) to producea heat-resistant resin film. The film thickness of the heat-resistantresin film was measured using SURFCOM 1400D (manufactured by TokyoSeimitsu Co., Ltd.) under the assumption that the refractive index was1.629. The prebaked film and the cured film thus produced were measuredwith respect to transmission spectra in a wavelength range of 300 to 800nm using an ultraviolet and visible spectrophotometer “MultiSpec-1500”(manufactured by Shimadzu Corporation). A prebaked film having such aresult that a light transmittance at a wavelength of 365 to 436 nm wasless than 50% was rated as “insufficient (C)”, and a prebaked filmhaving such a result that a light transmittance at a wavelength of 365to 436 nm was 50% or more was rated as “good (A)”. A cured film havingsuch a result that a light transmittance at a wavelength of 365 to 436nm was more than 10% was rated as “insufficient (C)”, and a cured filmhaving such a result that a light transmittance at a wavelength of 365to 436 nm was 10% or less was rated as “good (A)”. When theheat-resistant resin film does not have a thickness of 3.0 μm after aheat treatment, the light transmittance of the heat-resistant resin filmcan be determined by converting the thickness of the measuredheat-resistant resin film to 3.0 in accordance with the Lambert's law,and the transmission spectra were determined with respect to theheat-resistant resin film having a thickness of 3.0 μm.

(3) Formation of Relief Pattern

A varnish produced in each of Examples and Comparative Examples wasspin-coated on an 8-inch-square silicon wafer, and then the varnish wassubjected to a heat treatment (prebaking) at 120° C. for 2 minutes usinga hot plate (a coater/developer “Act-8”, manufactured by Tokyo ElectronLimited) to produce a prebaked film having a thickness of 3.7 μm. Theprebaked film was exposed to light at a light exposure amount of 0 to1000 mJ/cm² at steps of 20 mJ/cm² using an i line stepper (NSR-2005i9C,manufactured by Nikon Corporation) or a mask aligner (PEM-6M,manufactured by Union Optical Co., LTD.). Line & space patterns employedin the exposure to light, were as follows: 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 15, 20, 30, 50 and 100 mi. After the exposure to light, theresultant film was developed with a 2.38-wt % aqueoustetramethylammonium (TMAH) solution (ELM-D, manufactured by MitsubishiGas Chemical Company, Inc.) for 40 to 100 seconds, and was then rinsedwith purified water to form a relief pattern. The film thicknesses afterthe prebaking and the development were measured using an interferometertype film thickness measurement system Lambda Ace STM-602 (manufacturedby Dainippon Screen Manufacturing Co. Ltd.) under the assumption thatthe refractive index was 1.629.

(4) Calculation of Sensitivity

A minimum light exposure amount at which 50 μm-wide line-and-space (L/S)patterns were formed at a ratio of 1:1 after exposure to light anddevelopment was determined as a value of sensitivity.

(Synthesis Example 1) Compound Whose Maximum Absorption WavelengthShifts by Heat Treatment (I-1)

Under a dry nitrogen stream, tetrahydrofuran (abbreviated as “THF”,hereinafter) (50 g) was added to2,2′-dihydroxy-4,4′-dimethoxybenzophenone (product name: SEESORB107,manufactured by Shipro Kasei Kaisha, Ltd., maximum absorptionwavelength: 347 nm) (5.49 g) (0.020 mole), and the resultant solutionwas stirred at 40° C. to dissolve in each other. Subsequently, aceticanhydride (4.08 g) (0.040 mole) and N,N-dimethyl-4-aminopyridine (0.24g) (0.002 mole) were added to the solution, and the resultant solutionwas stirred at 40° C. for 2 hours. After the completion of the stirring,the solution was introduced into water (1 L), and precipitates of apolymer solid material were collected by filtration. The precipitateswere washed with water (500 mL) three times, and the collected polymersolid material was dried with a vacuum drier at 50° C. for 72 hours toproduce a compound whose maximum absorption wavelength shifts by a heattreatment (I-1, maximum absorption wavelength: 282 nm).

(Synthesis Example 2) Compound Whose Maximum Absorption WavelengthShifts by Heat Treatment (I-2)

Under a dry nitrogen stream, THF (50 g) was added to2,2′-dihydroxy-4,4′-dimethoxybenzophenone (product name: SEESORB107,manufactured by Shipro Kasei Kaisha, Ltd., maximum absorptionwavelength: 347 nm) (5.49 g) (0.020 mole), and the resultant solutionwas stirred at 40° C. to dissolve in each other. Subsequently, aceticanhydride (2.04 g) (0.020 mole) and N,N-dimethyl-4-aminopyridine (0.24g) (0.002 mole) were added to the solution, and the resultant solutionwas stirred at 40° C. for 2 hours. After the completion of the stirring,the solution was introduced into water (1 L), and precipitates of apolymer solid material were collected by filtration. The precipitateswere washed with water (500 mL) three times, and the collected polymersolid material was dried with a vacuum drier at 50° C. for 72 hours toproduce a compound whose maximum absorption wavelength shifts by a heattreatment (I-2, maximum absorption wavelength: 322 nm).

(Synthesis Example 3) Compound Whose Maximum Absorption WavelengthShifts by Heat Treatment (I-3)

Under a dry nitrogen stream, N-methyl pyrrolidone (abbreviated as “NMP”,hereinafter) (50 g) was added to2,2′-dihydroxy-4,4′-dimethoxybenzophenone (product name: SEESORB107,manufactured by Shipro Kasei Kaisha, Ltd., maximum absorptionwavelength: 347 nm) (5.49 g) (0.020 mole), and the resultant solutionwas stirred at 40° C. to dissolve in each other. Subsequently,di-tert-butyl dicarbonate (abbreviated as “t-Boc₂O”, hereinafter) (8.73g) (0.040 mole) and N,N-dimethyl-4-aminopyridine (0.24 g) (0.002 mole)were added to the solution, and the resultant solution was stirred at40° C. for 2 hours. After the completion of the stirring, the solutionwas introduced into water (1 L), and precipitates of a polymer solidmaterial were collected by filtration. The precipitates were washed withwater (500 mL) three times, and the collected polymer solid material wasdried with a vacuum drier at 50° C. for 72 hours to produce a compoundwhose maximum absorption wavelength shifts by a heat treatment (I-3,maximum absorption wavelength: 282 nm).

(Synthesis Example 4) Compound Whose Maximum Absorption WavelengthShifts by Heat Treatment (I-4)

Under a dry nitrogen stream, NMP (50 g) was added to2,2′-dihydroxy-4,4′-dimethoxybenzophenone (product name: SEESORB107,manufactured by Shipro Kasei Kaisha, Ltd., maximum absorptionwavelength: 347 nm) (5.49 g) (0.020 mole), and the resultant solutionwas stirred at 40° C. to dissolve in each other. Subsequently, t-Boc₂O(4.37 g) (0.020 mole) and N,N-dimethyl-4-aminopyridine (0.24 g) (0.002mole) were added to the solution, and the resultant solution was stirredat 40° C. for 2 hours. After the completion of the stirring, thesolution was introduced into water (1 L), and precipitates of a polymersolid material were collected by filtration. The precipitates werewashed with water (500 mL) three times, and the collected polymer solidmaterial was dried with a vacuum drier at 50° C. for 72 hours to producea compound whose maximum absorption wavelength shifts by a heattreatment (I-4, maximum absorption wavelength: 324 nm).

(Synthesis Example 5) Compound Whose Maximum Absorption WavelengthShifts by Heat Treatment (I-5)

Under a dry nitrogen stream, NMP (50 g) was added to2,2-dihydroxy-4,4′-dimethoxybenzophenone (product name: SEESORB107,manufactured by Shipro Kasei Kaisha, Ltd., maximum absorptionwavelength: 347 nm) (5.49 g) (0.020 mole), and the resultant solutionwas stirred at 40° C. to dissolve in each other. Subsequently, butylisocyanate (3.96 g) (0.040 mole) and N,N-dimethyl-4-aminopyridine (0.24g) (0.002 mole) were added to the solution, and the resultant solutionwas stirred at 40° C. for 2 hours. After the completion of the stirring,the solution was introduced into water (1 L), and precipitates of apolymer solid material were collected by filtration. The precipitateswere washed with water (500 mL) three times, and the collected polymersolid material was dried with a vacuum drier at 50° C. for 72 hours toproduce a compound whose maximum absorption wavelength shifts by a heattreatment (I-5, maximum absorption wavelength: 280 nm).

(Synthesis Example 6) Compound Whose Maximum Absorption WavelengthShifts by Heat Treatment (I-6)

Under a dry nitrogen stream, NMP (50 g) was added to2,2′-dihydroxy-4,4′-dimethoxybenzophenone (product name: SEESORB107,manufactured by Shipro Kasei Kaisha, Ltd., maximum absorptionwavelength: 347 nm) (5.49 g) (0.020 mole), and the resultant solutionwas stirred at 40° C. to dissolve in each other. Subsequently, butylisocyanate (1.98 g) (0.020 mole) and N,N-dimethyl-4-aminopyridine (0.24g) (0.002 mole) were added to the solution, and the resultant solutionwas stirred at 40° C. for 2 hours. After the completion of the stirring,the solution was introduced into water (1 L), and precipitates of apolymer solid material were collected by filtration. The precipitateswere washed with water (500 mL) three times, and the collected polymersolid material was dried with a vacuum drier at 50° C. for 72 hours toproduce a compound whose maximum absorption wavelength shifts by a heattreatment (I-6, maximum absorption wavelength: 325 nm).

(Synthesis Example 7) Compound Whose Maximum Absorption WavelengthShifts by Heat Treatment (I-7)

Under a dry nitrogen stream, NMP (50 g) was added to2,2′,4,4′-tetrahydroxylbenzophenone (product name: SEESORB106,manufactured by Shipro Kasei Kaisha, Ltd., maximum absorptionwavelength: 350 nm) (4.92 g) (0.020 mole), and the resultant solutionwas stirred at 40° C. to dissolve in each other. Subsequently, aceticanhydride (8.17 g) (0.080 mole) and N,N-dimethyl-4-aminopyridine (0.48g) (0.004 mole) were added to the solution, and the resultant solutionwas stirred at 40° C. for 2 hours. After the completion of the stirring,the solution was introduced into water (1 L), and precipitates of apolymer solid material were collected by filtration. The precipitateswere washed with water (500 mL) three times, and the collected polymersolid material was dried with a vacuum drier at 50° C. for 72 hours toproduce a compound whose maximum absorption wavelength shifts by a heattreatment (I-7, maximum absorption wavelength: 280 nm).

(Synthesis Example 8) Compound Whose Maximum Absorption WavelengthShifts by Heat Treatment (I-8)

Under a dry nitrogen stream, NMP (50 g) was added to2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole (product name: SEESORB707,manufactured by Shipro Kasei Kaisha, Ltd., maximum absorptionwavelength: 345 nm) (6.79 g) (0.020 mole), and the resultant solutionwas stirred at 40° C. to dissolve in each other. Subsequently, aceticanhydride (2.04 g) (0.020 mole) and N,N-dimethyl-4-aminopyridine (0.48g) (0.004 mole) were added to the solution, and the resultant solutionwas stirred at 40° C. for 2 hours. After the completion of the stirring,the solution was introduced into water (1 L), and precipitates of apolymer solid material were collected by filtration. The precipitateswere washed with water (500 mL) three times, and the collected polymersolid material was dried with a vacuum drier at 50° C. for 72 hours toproduce a compound whose maximum absorption wavelength shifts by a heattreatment (I-8, maximum absorption wavelength: 315 nm).

(Synthesis Example 9) Compound Whose Maximum Absorption WavelengthShifts by Heat Treatment (I-9)

Under a dry nitrogen stream, NMP (50 g) was added to2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3-5-triazine(product name: TINUVIN460, manufactured by BASF, maximum absorptionwavelength: 350 nm) (12.6 g) (0.020 mole), and the resultant solutionwas stirred at 40° C. to dissolve in each other. Subsequently, aceticanhydride (4.08 g) (0.040 mole) and N,N-dimethyl-4-aminopyridine (0.48g) (0.004 mole) were added to the solution, and the resultant solutionwas stirred at 40° C. for 2 hours. After the completion of the stirring,the solution was introduced into water (1 L), and precipitates of apolymer solid material were collected by filtration. The precipitateswere washed with water (500 mL) three times, and the collected polymersolid material was dried with a vacuum drier at 50° C. for 72 hours toproduce a compound whose maximum absorption wavelength shifts by a heattreatment (I-9, maximum absorption wavelength: 285 nm).

(Synthesis Example 10) Compound Whose Maximum Absorption WavelengthShifts by Heat Treatment (I-10)

Under a dry nitrogen stream, THF (50 g) was added to4,5-dihydroxyanthraquinone-2-carboxylic acid (maximum absorptionwavelength: 430 nm) (5.68 g) (0.020 mole), and the resultant solutionwas stirred at 40° C. to dissolve in each other. Subsequently, aceticanhydride (4.08 g) (0.040 mole) and N,N-dimethyl-4-aminopyridine (0.48g) (0.004 mole) were added to the solution, and the resultant solutionwas stirred at 40° C. for 2 hours. After the completion of the stirring,the solution was introduced into water (1 L), and precipitates of apolymer solid material were collected by filtration. The precipitateswere washed with water (500 mL) three times, and the collected polymersolid material was dried with a vacuum drier at 50° C. for 72 hours toproduce a compound whose maximum absorption wavelength shifts by a heattreatment (I-10, maximum absorption wavelength: 338 nm).

(Synthesis Example 11) Synthesis of Hydroxyl-Group-Containing DiamineCompound

2,2-Bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured byCentral Glass Co., Ltd., abbreviated as “BAHF”, hereinafter) (18.3 g)(0.05 mole) was dissolved in acetone (100 mL) and propylene oxide(manufactured by Tokyo Chemical Industry Co., Ltd.) (17.4 g) (0.3 mole),and the resultant solution was cooled to −15° C. To the resultantsolution was dropwisely added a solution prepared by dissolving3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co.,Ltd.) (20.4 g) (0.11 mole) in acetone (100 mL). After the completion ofthe dropwise addition, the solution was stirred at −15° C. for 4 hoursand then warmed to room temperature. A precipitated white solid materialwas filtered off and then dried in vacuo at 50° C.

The white solid material thus produced (30 g) was introduced into a300-mL stainless autoclave and was then dispersed in methyl cellosolve(250 mL), and then 5% palladium-carbon (manufactured by Wako PureChemical Industries, Ltd.) (2 g) was added thereto. Hydrogen wasintroduced into the reaction solution with a balloon to perform areduction reaction at room temperature. After about 2 hours, it wasconfirmed that the balloon could not shrink any more, and the reactionwas terminated. After the completion of the reaction, the reactionsolution was filtered to remove the palladium compound that was acatalyst, and then the filtrate was concentrated with a rotaryevaporator to produce a hydroxyl-group-containing diamine compoundrepresented by the following formula.

(Synthesis Example 12) Synthesis of Polyamic Acid Ester (A1-1)

Under a dry nitrogen stream, the hydroxyl-group-containing diamine (57.4g) (0.095 mole) produced in Synthesis Example 11 and1,3-bis(3-aminopropyl)tetramethyldisiloxane (abbreviated as “SiDA”,hereinafter) (1.24 g) (0.005 mole) were dissolved in NMP (200 g).4,4′-Oxydiphthalic anhydride (abbreviated as “ODPA”, hereinafter) (31.0g) (0.1 mole) was added to the solution, and the resultant solution wasstirred at 40° C. for 2 hours. Subsequently, a solution prepared bydiluting dimethylformamide dimethyl acetal (manufactured by MitsubishiRayon Co., Ltd., abbreviated as “DFA”, hereinafter) (7.14 g) (0.06 mole)with NMP (5 g) was dropwisely added to the solution over 10 minutes.After the dropwise addition, the stirring of the resultant solution wascontinued 40° C. for 2 hours. After the completion of the stirring, thesolution was introduced into water (2 L), and then precipitates of apolymer solid material were collected by filtration. The precipitateswere further washed with water (2 L) three times, and then the collectedpolymer solid material was dried with a vacuum drier at 50° C. for 72hours to produce a polyamic acid ester (A1-1).

(Synthesis Example 13) Synthesis of Quinone Diazide Compound (C-1)

Under a dry nitrogen stream,4,4′-[1-[4-[1-(4-hydroxyphenyl-1)-1-methylethyl]phenyl]ethylidene]bisphenol(manufactured by Honshu Chemical Industry Co., Ltd., abbreviated as“TrisP-PA”, hereinafter) (21.22 g) (0.05 mole) and5-naphthoquinonediazidesulfonic acid chloride (NAC-5, manufactured byToyo Gosei Co., Ltd) (26.8 g) (0.1 mole) were dissolved in 1,4-dioxane(450 g) at room temperature. Triethylamine (12.65 g) that was mixed with1,4-dioxane (50 g) was dropwisely added to the solution in such a mannerthat the temperature in the system did not become 35° C. or higher.After the dropwise addition, the solution was stirred at 40° C. for 2hours. A triethylamine salt was filtered off, and a filtrate wasintroduced into water. Subsequently, precipitates were collected byfiltration and then washed with 1% aqueous hydrochloric acid (1 L).Subsequently, the washed product was further washed with water (2 L) twotimes. The precipitates were dried with a vacuum drier to produce aquinone diazide compound (C-1) represented by the following formula.

Example 1

The compound (I-1) (2 g) (maximum absorption wavelength: 282 nm)produced in Synthesis Example 1 and the polyamic acid ester (A1-1) (10g) produced in Synthesis Example 12 were weighed and then dissolved inγ-butyrolactone (abbreviated as “GBL”, hereinafter) (40 g) to produce avarnish of a polyimide precursor composition. The varnish was used tomeasure light transmittance, and the light transmittance at a wavelengthwithin 365 to 436 nm before a heat treatment was 50% or more. The lighttransmittance at a wavelength within 350 to 378 nm after the heattreatment was 10% or less.

(Examples 2 to 3), (Comparative Examples 1 to 4)

Varnishes were produced in the same procedure as in Example 1, exceptthat the types and amounts of the compounds were as shown in Table 9.Each of the varnishes was used to measure the transmittances before andafter a heat treatment. The evaluation results are shown in Table 10.

TABLE 9 Components of resin composition (I) Compound of which maximumabsorption wavelength shifts by (C) Photo-acid (A) Alkali-soluble resinheat treatment generator (D) Solvent Other compound (content) (content)(content) (content) (content) Example 1 (A1-1) I-1 — GBL — (10 g) (2 g)(40 g) Example 2 (A1-1) I-2 — GBL — (10 g) (2 g) (40 g) Example 3 (A1-1)I-7 — GBL — (10 g) (2 g) (40 g) Comparative (A1-1) — — GBL SEESORB 107Example 1 (10 g) (40 g) (1 g) Comparative (A1-1) — — GBL SEESORB 106Example 2 (10 g) (40 g) (1 g) Comparative (A1-1) — — GBL SEESORB 707Example 3 (10 g) (40 g) (1 g) Comparative (A1-1) — — GBL TINUVIN 460Example 4 (10 g) (40 g) (1 g)

TABLE 10 Wavelength at which Wavelength at which transmittanceAbsorption maximum transmittance becomes 50% or becomes 10% or lessafter heat wavelength of component (I) more before heat treatmenttreatment (nm) (nm) (nm) Example 1 282 A (365-436) A (365-378) Example 2322 A (365-436) A (365-379) Example 3 280 A (365-436) A (365-375)Comparative — C (395-436) A (365-380) Example 1 Comparative — C(400-436) A (365-385) Example 2 Comparative — C (390-436) A (365-376)Example 3 Comparative — C (395-436) A (365-382) Example 4

In each of Examples 2 to 3 which were resin compositions each containing(A) an alkali-soluble resin, (I) a compound whose maximum absorptionwavelength shifts by a heat treatment and (D) a solvent, thetransmittance at a wavelength within 365 to 436 nm before a heattreatment was 50% or more. The transmittance in some range having awavelength of 380 nm or less among wavelengths within 365 to 436 nmafter the heat treatment was 10% or less. In each of ComparativeExamples 1 to 4 in each of which a component (I) was not contained and acompound having such a structure that a protecting group in a component(I) was removed was used, there was observed a range in which thetransmittance was lower than 50% in the wavelength range of 365 to 436nm.

Example 4

The compound (I-1) (2 g) (maximum absorption wavelength: 282 nm)produced in Synthesis Example 1, the polyamic acid ester (A1-1) (10 g)produced in Synthesis Example 12 and the quinone diazide compound (C-1)(3 g) produced in Synthesis Example 13 were weighed and then dissolvedin γ-butyrolactone (abbreviated as “GBL”, hereinafter) (40 g) to producea varnish of a polyimide precursor composition. The varnish was used toevaluate photosensitiveness, and the sensitivity to i line was 280mJ/cm² and the sensitivity to ghi line was 130 mJ/cm². The lighttransmittance at a wavelength within 365 to 378 nm after the heattreatment was 10% or less.

(Examples 5 to 16), (Comparative Examples 5 to 9)

Varnishes were produced in the same procedure as in Example 4, exceptthat the types and amounts of the compounds were as shown in Tables 11and 13. Each of the varnishes was used to evaluate photosensitive andmeasure the transmittance after a heat treatment. The evaluation resultsare shown in Tables 12 and 14.

TABLE 11 Components of resin composition (I) Compound of which maximumabsorption wavelength shifts by (C) Photo-acid (A) Alkali-soluble resinheat treatment generator (D) Solvent Other compound (content) (content)(content) (content) (content) Example 4 (A1-1) I-1 C-1 GBL — (10 g) (2g) (3 g) (40 g) Example 5 (A1-1) I-2 C-1 GBL — (10 g) (2 g) (3 g) (40 g)Example 6 (A1-1) I-3 C-1 GBL — (10 g) (2 g) (3 g) (40 g) Example 7(A1-1) I-4 C-1 GBL — (10 g) (2 g) (3 g) (40 g) Example 8 (A1-1) I-5 C-1GBL — (10 g) (2 g) (3 g) (40 g) Example 9 (A1-1) I-6 C-1 GBL — (10 g) (2g) (3 g) (40 g) Example (A1-1) I-7 C-1 GBL — 10 (10 g) (2 g) (3 g) (40g) Example (A1-1) I-8 C-1 GBL — 11 (10 g) (2 g) (3 g) (40 g) Example(A1-1) I-9 C-1 GBL — 12 (10 g) (2 g) (3 g) (40 g) Example (A1-1) I-10C-1 GBL — 13 (10 g) (2 g) (3 g) (40 g) Example (A1-1) I-1 C-1 GBL — 14(10 g) (2 g) (3 g) (40 g) I-10 (2 g) Example (A1-1) I-1 C-1 GBL ValifastYellow 4120(0.5 g) 15 (10 g) (2 g) (3 g) (40 g) (absorption maximumwavelength: 445 nm) Valifast RED 3311(0.6 g) (absorption maximumwavelength: 525 nm) Valifast Blue 2620(0.6 g) (absorption maximumwavelength: 690 nm) Example (A1-1) I-1 C-1 GBL Plast Yellow8070(0.3 g)16 (10 g) (2 g) (3 g) (40 g) (absorption maximum wavelength: 445 nm) OilScarlet5206(0.6 g) (absorption maximum wavelength: 515 nm) PlastBlue8540(1.2 g) (absorption maximum wavelength: 645 nm)

TABLE 12 photosensitivity Absorption maximum properties wavelength ofWavelength at which transmittance Absorption maximum SensitivitySensitivity component (I) becomes 10% or less after heat wavelength ofcomponent (I) (i line) (ghi line) after heat treatment treatment (nm)(mJ/cm²) (mJ/cm²) (nm) (nm) Example 4 282 280 130 347 A (365-378)Example 5 322 340 160 347 A (365-379) Example 6 282 280 130 347 A(365-375) Example 7 324 350 160 347 A (365-377) Example 8 280 270 130347 A (365-378) Example 9 325 340 160 347 A (365-377) Example 280 270130 350 A (365-368) 10 Example 315 320 150 345 A (365-374) 11 Example285 280 130 350 A (365-380) 12 Example 338 420 180 430 A (390-436) 13Example 282, 338 360 160 347, 430 A (365-436) 14 Example 282 360 160 347A (365-375) 15 Example 282 360 160 347 A (365-375) 16

TABLE 13 Components of resin composition (I) Compound of which maximumabsorption wavelength shifts by (C) Photo-acid (A) Alkali-soluble resinheat treatment generator (D) Solvent Other compound (content) (content)(content) (content) (content) Comparative (A1-1) — C-1 GBL — Example 5(10 g) (3 g) (40 g) Comparative (A1-1) — C-1 GBL SEESORB 107 Example 6(10 g) (3 g) (40 g) (1 g) Comparative (A1-1) — C-1 GBL SEESORB 106Example 7 (10 g) (3 g) (40 g) (1 g) Comparative (A1-1) — C-1 GBL SEESORB707 Example 8 (10 g) (3 g) (40 g) (1 g) Comparative (A1-1) — C-1 GBLTINUVIN 460 Example 9 (10 g) (3 g) (40 g) (1 g)

TABLE 14 photosensitivity properties Absorption maximum Wavelength atwhich transmittance Absorption maximum Sensitivity Sensitivitywavelength of component (I) becomes 10% or less after heat wavelength ofcomponent (I) (i line) (ghi line) after heat treatment treatment (nm)(mJ/cm²) (mJ/cm²) (nm) (nm) Comparative — 220 120 — C (<350) Example 5Comparative — >1000 300 — A (365-380) Example 6 Comparative — >1000 300— A (365-385) Example 7 Comparative — >1000 300 — A (365-376) Example 8Comparative — >1000 340 — A (365-382) Example 9

In each of Examples 5 to 12 which were resin compositions eachcontaining (A) an alkali-soluble resin, (I) a compound whose maximumabsorption wavelength shifts by a heat treatment, (C) a photo-acidgenerator, (D) a solvent and other component and having positive-workingphotosensitiveness, the sensitivity to i line was 350 mJ/cm² or less andthe sensitivity to ghi line was 180 mJ/cm² or less. The transmittance ina range having a wavelength of 380 nm or less in the wavelength range of365 to 436 nm after the heat treatment was 10% or less. In Example 13 inwhich the compound (I-10) produced in Synthesis Example 10 was used, thesensitivity to i line was 420 mJ/cm² and the sensitivity to ghi line was180 mJ/cm². With respect to the transmittance after the heat treatment,the transmittance at a wavelength range of 390 nm or more, amongwavelengths of 365 to 436 nm, was 10% or less. In Example 14 in whichthe compound (I-1) produced in Synthesis Example 1 and the compound(I-10) produced in Synthesis Example 10 were used, the sensitivity to iline was 360 mJ/cm² and the sensitivity to ghi line was 160 mJ/cm². Withrespect to the transmittance after the heat treatment, the transmittanceat a wavelength within the whole wavelength range of 365 to 436 nm was10% or less. In each of Examples 15 and 16 in each of which acombination of three types of dyes having different maximum absorptionwavelengths from one another was used as the component (J), thesensitivity to i line was 360 mJ/cm² and the sensitivity to ghi line was160 mJ/cm². With respect to the transmittance after the heat treatment,the transmittance at a wavelength within a wavelength range of 380 nm orless among wavelengths of 365 to 436 nm was 10% or less. Because of theaddition of the dyes, the products were blackened and had OD values of0.2. In Comparative Example 5 in which the component (I) was notcontained, the transmittance at a wavelength within the whole wavelengthrange of 350 to 460 nm after the heat treatment was 10% or more. InComparative Examples 6 to 9 in each of which the component (I) was notcontained and a compound having such a structure that a protecting groupis removed from the component (I) was used instead, the sensitivity wassignificantly deteriorated.

Example 17

Bottom-gate-type oxide TFTs, each of which was designed in such a manneras to have a degree of resolution of 200 ppi, were formed on a glasssubstrate, and then an insulating film made from Si₃N₄ was formed insuch a manner as to cover the TFTs. Subsequently, contact holes wereformed in the insulating film, and then wiring lines (height: 1.0 μm)which were to be respectively connected to the TFTs through the contactholes was formed on the insulating film. The wiring lines were intendedto connect the TFTs to each other or connect organic EL elements thatwere formed in the latter step to the TFTs.

For the purpose of planarizing projections and depressions whichoccurred as the result of the formation of the wiring lines, aplanarization film was formed on the insulating film in such a manner asto fill the projections and depressions occurring as the result of theformation of the wiring line. The formation of the planarization film onthe insulating film was carried out by spin-coating a varnish of aphotosensitive polyimide precursor composition produced in any one ofExamples 4 to 16 onto a substrate, then pre-baking the varnish on a hotplate at 120° C. for 2 minutes, and then subjecting the pre-bakedproduct to a heat treatment under a nitrogen flow at 250° C. for 60minutes. The coatability during the application of the varnish was good,and the occurrence of wrinkling or cracking was not observed in aheat-resistant resin film that was produced after the exposure to light,development and baking of the varnish. The average difference in levelof the wiring lines was 500 nm, and the film thickness of theplanarization film produced was 2000 nm.

The photodeterioration upon the irradiation of the oxide TFT devicehaving the planarization film provided therein with light under negativebias stress was measured. The fluctuation in threshold voltage (i.e.,the shift of a threshold voltage) before and after the irradiation withlight was reduced, and a photodeterioration reduction effect wasconfirmed.

Example 18

Bottom-gate-type oxide TFTs, each of which was designed in such a manneras to have a degree of resolution of 200 ppi, were formed on a glasssubstrate, and then an insulating film made from Si₃N₄ was formed insuch a manner as to cover the TFTs. Subsequently, contact holes wereformed in the insulating film, and then wiring lines (height: 1.0 μm)which were to be respectively connected to the TFTs through the contactholes were formed on the insulating film. The wiring lines were intendedto connect the TFTs to each other or connect organic EL elements thatwere formed in the latter step to the TFTs.

For the purpose of planarizing projections and depressions whichoccurred as the result of the formation of the wiring lines, aplanarization film was formed on the insulating film in such a manner asto fill the projections and depressions occurring as the result of theformation of the wiring line. The formation of the planarization film onthe insulating film was carried out by spin-coating a varnish of aphotosensitive polyimide precursor composition produced in any one ofExamples 4 to 16 onto a substrate, then pre-baking the varnish on a hotplate at 120° C. for 2 minutes, and then subjecting the pre-bakedproduct to a heat treatment under a nitrogen flow at 250° C. for 60minutes. The coatability during the application of the varnish was good,and the occurrence of wrinkling or cracking was not observed in aheat-resistant resin film that was produced after the exposure to light,development and baking of the varnish. The average difference in levelof the wiring lines was 500 nm, and the film thickness of theplanarization film produced was 2000 nm.

Subsequently, top-emission-type organic EL elements were formed on theplanarization film. First, bottom electrodes made from ITO were formedon the planarization film by sputtering in such a manner as to berespectively connected to the wiring lines through the contact holes.Subsequently, a resist was applied, and the resultant product waspre-baked and then was exposed to light through a mask having a desiredpattern to develop the pattern. A pattern processing was carried out bywet etching using an ITO etchant and using the resist pattern as a mask.Subsequently, the resist pattern was stripped with a resist strippingsolution (a mixed solution of monoethanolamine and DMSO). The bottomelectrodes produced in this manner correspond to anodes of the organicEL elements.

Subsequently, an insulating layer having a shape capable of covering theperipheries of the bottom electrodes was formed. For the formation ofthe insulating layer, a varnish of a photosensitive polyimide precursorcomposition produced in any one of Examples 4 to 16 was also used. Whenthe insulating layer is provided, it becomes possible to prevent theoccurrence of shorting out between bottom electrodes and an upperelectrode produced in the latter step. The insulating layer waspatterned and then subjected to a heat treatment at 250° C. for 60minutes to form an insulating layer having proper absorption at awavelength around 450 nm.

On the resultant product, a hole-transport layer, a red organiclight-emitting layer, a green organic light-emitting layer, a blueorganic light-emitting layer and an electron-transport layer were formedin this order by deposition through a desired mask pattern in a vacuumevaporator. Subsequently, an upper electrode made from Al was formedover the whole upper surface of the substrate. The upper electrodecorresponds to a cathode of the organic EL elements. The substrate wasremoved from the evaporator, and then was sealed by adhering thesubstrate to a glass substrate for sealing use with anultraviolet-ray-curable epoxy resin.

In the above-mentioned manner, an active-matrix-type organic EL displaydevice, in which TFTs for driving organic EL elements were respectivelyconnected to the organic EL elements, was produced. A voltage wasapplied to the device through a driving circuit, and good luminescencewas observed.

DESCRIPTION OF REFERENCE SIGNS

-   -   1: TFT    -   2: Wiring line    -   3: Insulating film    -   4: Planarization film    -   5: ITO    -   6: Substrate    -   7: Contact hole    -   8: Insulating layer

1. A resin composition which is configured such that, when the resincomposition is formed into a resin composition film that has a thicknessof 3.0 μm after a heat treatment at a temperature within the range from200 to 350° C., the resin composition film forms a heat-resistant resinfilm having a light transmittance of 50% or more at a wavelength of 365to 436 nm before the heat treatment and having a light transmittance of10% or less at a wavelength of 365 to 436 nm after the heat treatment.2. The resin composition according to claim 1, wherein, when the resincomposition is formed into a resin composition film having a thicknessof 2.0 μm after a heat treatment at a temperature within the range from200 to 350° C., the resin composition film forms a heat-resistant resinfilm having a light transmittance of 50% or more at a wavelength of 365to 436 nm before the heat treatment and having a light transmittance of5% or less at a wavelength of 350 to 460 nm after the heat treatment. 3.The resin composition according to claim 1, additionally containing aphoto-acid generator and having positive-working photosensitivity.
 4. Aresin composition having positive-working photosensitivity andcomprising (A1) a polyimide, a polybenzoxazole, a polyimide precursor ora polybenzoxazole precursor, (A3) a phenolic resin and/or apolyhydroxystyrene resin, (B) a thermally color-developing compound, (C)a photo-acid generator, and (D) a solvent, wherein the component (A3) iscontained in an amount of 5 to 50 parts by weight inclusive relative to100 parts by weight of the component (A1).
 5. A resin composition havingpositive-working photosensitivity and comprising (A2) a resin havingsuch a backbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom, (A3) a phenolicresin and/or a polyhydroxystyrene resin, (B) a thermallycolor-developing compound, (C) a photo-acid generator, and (D) asolvent, wherein the component (A3) is contained in an amount of 5 to 50parts by weight inclusive relative to 100 parts by weight of thecomponent (A2).
 6. The resin composition according to claim 4, whereinthe thermally color-developing compound (B) is ahydroxy-group-containing compound having a triarylmethane backbone. 7.The resin composition according to claim 4, additionally containing (E)a dye and/or a pigment.
 8. The resin composition according to claim 4,additionally containing (F) a compound having 3 to 6 thermallycrosslinkable groups per molecule.
 9. A resin composition havingpositive-working photosensitivity and comprising (A) an alkali-solubleresin, (I) a compound whose maximum absorption wavelength shifts by aheat treatment, (C) a photo-acid generator, and (D) a solvent.
 10. Theresin composition having positive-working photosensitivity according toclaim 9, wherein the alkali-soluble resin (A) is a polyimide, apolybenzoxazole, a polyimide precursor or a polybenzoxazole precursor.11. The resin composition having positive-working photosensitivityaccording to claim 9, wherein the alkali-soluble resin (A) comprises atleast one alkali-soluble resin selected from: a resin having such abackbone structure that two cyclic structures are bonded to acyclic-structure-constituting quaternary carbon atom; and a phenolicresin and/or a polyhydroxystyrene resin.
 12. The resin compositionhaving positive-working photosensitivity according to claim 9, whereinthe compound (I) whose maximum absorption wavelength shifts by a heattreatment has a maximum absorption wavelength of 340 nm or more and lessthan 450 nm after a heat treatment.
 13. The resin composition havingpositive-working photosensitivity according to claim 9, wherein thecompound (I) whose maximum absorption wavelength shifts by a heattreatment is a compound which has one or more phenolic hydroxyl groupsand in which one, several or all of the phenolic hydroxyl groups arerespectively protected by protecting groups.
 14. The resin compositionhaving positive-working photosensitivity according to claim 13, whereinthe compound (I) whose maximum absorption wavelength shifts by a heattreatment has one or more phenolic hydroxyl groups and each of theprotecting groups which respectively protect one, several or all of thephenolic hydroxyl groups is a heat-labile group or an acid-labile group.15. The resin composition having positive-working photosensitivityaccording to claim 14, wherein the compound (I) whose maximum absorptionwavelength shifts by a heat treatment has one or more phenolic hydroxylgroups and a heat-labile group or an acid-labile group which protectseach of one, several or all of the phenolic hydroxyl groups isrepresented by any one of general formula (8) to (11):

(in general formula (8), R⁵⁹ to R⁶¹ may be the same as one another orone or some of R⁵⁹ to R⁶¹ may be different from the others, andindependently represent a hydrogen atom or a monovalent hydrocarbongroup having 1 or more carbon atoms; in general formula (9), nrepresents 0 or 1; in general formula (10), R⁶² represents a monovalenthydrocarbon group having 1 to 20 carbon atoms; and in general formula(11), Z represents a hydrogen atom, a sulfur atom or —N(R⁶³)—R⁶⁴,represents a monovalent hydrocarbon group having 1 to 20 carbon atoms,and R⁶³ represents a hydrogen atom or a monovalent hydrocarbon grouphaving 1 to 20 carbon atoms).
 16. The resin composition havingpositive-working photosensitivity according to claim 9, wherein thecompound (I) whose maximum absorption wavelength shifts by a heattreatment is a non-condensed polycyclic compound or a condensedpolycyclic compound.
 17. The resin composition having positive-workingphotosensitivity according to claim 9, wherein the compound (I) whosemaximum absorption wavelength shifts by a heat treatment is anon-condensed polycyclic compound or a condensed polycyclic compoundeach having 2 to 8 inclusive of aromatic rings.
 18. The resincomposition having positive-working photosensitivity according to claim9, additionally containing (J) a compound which does not have anabsorption maximum at a wavelength of 340 nm or more and less than 436nm and has an absorption maximum at a wavelength of 436 to 750 nminclusive.
 19. The resin composition having positive-workingphotosensitivity according to claim 9, additionally containing (F) acompound having 3 to 6 thermally crosslinkable groups per molecule. 20.A method for producing a heat-resistant resin film, comprising the stepsof: applying a resin composition as recited in claim 1 onto a substrateto form a coating film; drying the coating film; exposing the driedphotosensitive resin film to light; developing the light-exposedphotosensitive resin film; and subjecting the developed photosensitiveresin film to a heat treatment.
 21. A method for producing aheat-resistant resin film, comprising the steps of: applying a resincomposition as recited in claim 1 onto a substrate using a slit nozzleto form a coating film; and drying the coating film under reducedpressure to form a photosensitive resin film.
 22. A display devicecomprising a substrate, a first electrode which is formed on thesubstrate, an insulating layer which is formed on the first electrode insuch a manner as to allow the first electrode to be partially exposed tolight, and a second electrode which is provided opposed to the firstelectrode, wherein the insulating layer is a heat-resistant resin filmproduced by a production method as recited in claim
 20. 23. A displaydevice comprising a substrate on which thin film transistors (TFTs) areformed, a planarization film which is provided in such a manner as tocover projections and depressions on the substrate, and display elementswhich are provided on the planarization film, wherein the planarizationfilm is a heat-resistant resin film produced by a production method asrecited in claim
 20. 24. A display device comprising a substrate onwhich oxide TFTs are formed as thin film transistors (TFTs), aplanarization film which is provided in such a manner as to coverprojections and depressions on the substrate, and display elements whichare provided on the planarization film, wherein the planarization filmis a heat-resistant resin film produced by a production method asrecited in claim
 20. 25. The display device according to claim 23,wherein the degree of resolution of each of the display elements is 200ppi or more.